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By G. R. Love, M. L. Picklesirner

THE use of color adds a new beauty, power, and versatility to metallography. This has been amply demonstrated in a number of public exhibits and on the walls of corporate, government, and university metallographic laboratories around the world. Indeed, in a number of cases, the color not only is of esthetic value but is scientifically essential to the competent examination of particular samples and systems. Optical strain analysis,' determination of true grain size in U-A1 alloys: phase identification in Nb-base alloys,3 analysis of transformation rates in heat-treated Nb-Zr alloys,4 measurement of solidification segregation in cast Nb-Zr alloys,' study of the intermediate phases in Nb/Sn diffusion couples,6 investigation of the oxidation kinetics at various surface orientations in single crystals,7'8 and a number of other research efforts9'10 would have been vastly more difficult without the extra clarity and distinction introduced by color—either the colors resulting from particular polarized light techniques or the interference colors obtained by oxidation. It is unfortunate that the beauty of colored micro-structures cannot be shared more widely, but the economics of publishing a technical magazine apparently prohibits color plates except under extraordinary circumstances. It is doubly unfortunate that no convenient, general method exists for communicating the information available in colored microstructures to the scientific community. True, in some instances the color changes observed are dramatic enough that direct black and white photography is adequate. In photoelastic stress analysis, several orders of interference fringes may be produced and it is frequently desirable to suppress the color effects (use monochromatic light) to simplify interpretation. On the other hand, relatively minute color variations may be readily detectable by eye, be of considerable assistance in interpreting a structure, and yet be enormously difficult to reduce to an unambiguous black and white print. In order to illustrate a possible compromise or solution to the above problems, we wish to show three black and white photographs of the same region of an Nb/Sn diffusion couple whose interpretation depends heavily upon use of color techniques. These micro-structures were obtained from a section through a rod consisting of commercial-purity niobium tubing filled with 99.995 pct Sn (melt-filled in 10"6 Torr vacuum). The composite rod, measuring 500 mm long, was bent into a hairpin shape and inserted into water-cooled copper grips in a vacuum high-temperature furnace. The rod was outgassed for 2 hr at a furnace temperature of 800°C and was further heated by self-resistance using a 2.2-kva ac power supply. The rod was raised to 1910°C over a 4+-hr period, held for 15 min, slow-cooled to 1500°C over a -hr period, and free-cooled to room temperature (all temperatures were measured with W5Re/W26Re thermocouple). Throughout the heat treatment the ambient pressure was kept below 8 x lo-' Torr. Metallographic preparation of the sample was completely conventional except that it was necessary to extend the grinding steps to remove damage in the brittle NbsSn phase introduced by sectioning. No satisfactory chemical or electrochemical etch has been found for these diffusion couples; of those which have been tried, any that attack the niobium-rich phases at all attack the tin-rich phases disastrously. However, the final polishing steps did produce a slight relief effect and this, coupled with anodizing, yielded excellent clarity in the microstructures for direct observation. The anodizing voltage was chosen to give maximum change in color per unit change in composition. In this case, indeed normally, this maximum sensitivity occurred in the blue-to-red color range. The pure niobium tube wall anodized to a relatively bright blue

Jan 1, 1967

Jan 1, 1880

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By George S. Rice

MANY studies on ground movement and subsidence have been carried on by members of the Institute during the past year, but only a few papers have reached maturity. Two of the mining schools of this country have continued their interest in ground movement research. At Columbia University School of Mines, Philip Bucky has continued his investigations, employing photoelastic methods and the use of his centrifugal apparatus for testing what he termed "the strength and behavior of mining structures." Helmut Landsberg, of The Pennsylvania State College, has developed a convergence recorder similar in principle to that used by the

Jan 1, 1936

By Frank T. Sisco

DURING the past year the iron and steel industry of the world as a whole operated on a satisfactory basis. No discoveries nor new processes of outstanding importance were announced either here or abroad, although rumors of such were persistent. In general, the efforts of operating and research men in the iron and steel industry seemed to be confined to improving quality and reducing cost, not a new aim, for the same efforts have been noted in nearly all of the annual reviews of the industry for at least fifty years. Most published papers on blast furnace or steel-making practice were of minor importance, at least when judged by the criterion of radical change in process or product. If the number of reports in the technical journals, or articles in the trade press, is used as a basis for comparison, continuous-mill sheet is still the most important single product of the industry; papers were published detailing the results of the investigation of various phases of the

Jan 1, 1938

By S. H. Ash, J. J. Forbes

Probably the newest thing in mining safety, or safety for mines, is the apparent dissatisfaction on the part of the mineral industries, as represented by both management and labor, and the general public of the Nation, with the safety record of the mining industry. This is reflected by published comments and papers in the technical press;l-9 in labor periodicals,10,11 in popular journals and periodicals,l2, 13 and in the daily press; also by discussions of the Safety Committees sponsored by the National Safety Council,9, 14-15 the American Mining Congress,l.l6 the American Institute of Mining and Metallurgical Engineers,2,4 the Mine Inspectors' Institute of Amerthe Coal Mining Institute of America,5 19 the American Standards Association, and others.20.21 Mining safety is a joint problem of management and the individual workman. Safety is not attained and will not be attained solely by laws, decrees, and commands because, if it could be done in this manner, acceptable mining safety would have been achieved long ago by the individual states in our Nation and by the nations abroad. The best safety performance is found at plants where management provides a safe environment for the workers; where supervision is efficient and super- visors, others concerned with promoting safety, and the individual worker know through training, experience, and personal contact the safe and unsafe practices of their field; and where the trained individual worker has become safety-minded by experience, quiet influence, unconscious suggestion, and personal guidance. Despite what may be said to the contrary, progress has been and is being made in mining safety. This is shown in Fig 1 to 4. It is beyond the scope of this paper to give possible reasons for the valleys and peaks in the fatal-injury rates. Some recent factors that appear to be contributing to the improvement in these rates are briefly discussed. Aside from mining equipment, "what's new in mining safety" for some mines has been in effect or was tried by others long ago. A safety pro- gram is a living thing; as such, it must be vitalized and continuously fed with enthusiasm, constructive action, and improvements. Because safety is concerned with human conduct, it is necessary to practice safety at all times; if not, it is soon forgotten, and accidents occur. Mining-safety Records The large employment and production concerned with anthracite contribute much to the mining-safety records of the mineral industry. Approximately 81,000 persons are. employed in this industry having mines concentrated in an area of 480 square miles in northeastern Pennsylvania. Because of the achievement of the anthracite industry in safety during 1948, the other branches of the mineral industry can profit by a study of what has been done to achieve that record. Where one mineral is produced by other large groups having methods of mining that are similar in many respects to the anthracite-mining methods, an achievement in such a large industry is important. Salient factors concerned with safetye in the anthracite industry are: no radical change has occurred in the mining-safety regulations pertaining to anthracite mines. Because anthracite mining is a branch of the coal-mining industry,

Jan 1, 1950

By Albert S. Trube

Increasing emphasis is being placed on the necessity for obtaining reasonably accurate estimates of the physical properties of reservoir fluids well in advance of more accurate laboratory data. One such factor is the isothermal coefficient of expansion of an undersaturated hydrocarbon liquid which may be contained in a particular reservoir. This coefficient, or liquid "compressibility", has often been assumed to be relatively insensitive and nearly constant. Although this assumption may be nearly correct in the case of high specific gravity liquids, it cannot apply in the case of medium to low specific gravity liquids. Any treatment of the nature of liquid compressibilities must give consideration to the variable nature of the isothermal expansion coefficient and the fact that it can be both pressure sensitive and temperature sensitive. The isothermal coefficient of expansion, or compressibility, of a substance is defined as -c = 1/V (?V/?p)T......(1) The value of Eq. 1 may be approximated for a finite pressure change by using the well-known relation, c = V1 - V1/Ve (p2-p1), ........(2) in which p1 > p1 and V2 > V2 and V1 + V2/2. The instantaneous compressibility may also be estimated from the slope of a curve on which log V is plotted vs pa. In this instance, it has been shown that c = In V1/V2/p2-p1 ...........(3) Eq. 3 may be used for variable compressibilities by plot-ting V vs p on semi-log paper. In this case, the instan-taneous or point compressibility is c = 2.303 m.......... . (4) in which m is the slope of the curve at a point in log cycles per psi. ISOTHERMAL COMPRESSIBILITY OF UNDERSATURATED LIQUID In the case of gases, the compressibility has been defined by Muskat' and others as Co = 1/p - ?z/z?p ..........(5) This was later generalized through application of the theorem of corresponding states' to co = 1/pr - (?z/z?pr) T8 ........(6) in which c, is defined as the pseudo-reduced compres-sibility and is numerically equal to (c.p,) and the sign is arbitrarily changed for mathematical convenience. Eq. 6 is general and applies to gases and liquids. In the case of liquids, c. = c1,pe, but if Eq. 6 is used, values of z and ?z/?p, must be determined for the liquid in question. The difficulty of obtaining accurate values of ?z/?p,, particularly in the region where T, is approaching 1.00, was pointed out in the previous paper'. This method of approach is unreliable for extension into computations of liquid compressibilities. On the other hand, c, can also be defined as follows: - Cr = 1/Vr (?Vr/?pr) Tr ......(7) and from which, Cr = 1/pr (?pr/?pr) Tr .....(8) In accordance with the theorem of corresponding states, Vr = V/Vr, p, = p/pr and pr = p/pr. Ref. 2 pro-vides an excellent source of reduced density, reduced pressure and reduced temperature data for a wide variety of fluids. For the purpose of this investigation, the set of fluids2 having ze = 0.27 was chosen because it in-cludes most of the heavier hydrocarbons usually found in those complex mixtures loosely defined as "reservoir oils". Data on undersaturated liquids in Ref. 2 were rearranged to conform with Eq. 8. To simplify the computation of cr, the isothermal p, data were plotted vs the log of pr, in which case for any straight line or tangent cr = 1/M pr pr .....(9)

Jan 1, 1958

Jan 1, 1903

THE opening session was held on Tuesday evening, February 17th, in the house of the American Society of Civil Engineers. The President of the Institute, Mr. E. B. Coxe, after a few introductory remarks, congratulating the members on the general prosperity in all the branches of the professions and manufactures represented by the Institute, called on Mr. E. F. Loiseau, of Philadelphia, for the first paper, On the Successful Manufacture of Compressed Fuel at Port Richmond, Philadelphia. Professor Prime called attention to the fact that the work of the United States Testing Board had been left unfinished at a point when valuable results had just been reached, and offered the following resolutions: WHEREAS, The American Institute of Mining Engineers has seen with regret that the work of the United States Testing Board has been suspended through the lack of an appropriation by Congress, which appropriation dues not seem likely to be renewed, and WHEREAS, It seems most important to the vital interests of our iron and steel manufactures that the experiments commenced by the United States Testing Board should be carried to successful completion ; Resolved, That a committee of three be appointed, to act with a like, committee to he appointed by the American Society of Civil Engineers, to carry out to completion the work commenced by the United States Testing Board. Resolved, That the American Society of Civil Engineers be requested to cooperate with this society by the appointment of a like committee. Resolved, That the committee have authority to request, in the name of the American Institute of Mining Engineers, contributions to a fund to be devoted to the completion of the experiments aforesaid. Resolved, That the Council of this Institute be authorized, whenever requested by the committee so appointed, to petition Congress for the free use of the testing machine at the United States Arsenal at Watertown. Resolved, That a committee be appointed by the President, to select the afore-said committee of experts. Resolved, That the President of the Institute have authority to fill any vacancies which may occur in the committee. The resolutions were unanimously adopted, and President Coxe appointed the following committee in accordance with the resolutions : Messrs. A. L. Holley, James Park, Jr., and J. F. Holloway. The President also appointed Messrs. Heinrich, Mickley, and Spils-

Jan 1, 1880

By E. M. Norris

Phosphate deposits are distributed widely over the earth's surface. Of the known areas of deposit, eight fields are of particular interest because of their vast reserves of high grade phosphatic material and the volume of their production that goes to the world's great consuming areas. These fields, in the order of their present economic importance, are situated respectively in Florida, French Morocco, Kola Peninsula of U.S.S.R., Tunisia and Algeria, Tennessee, Montana-Idaho-Wyoming-Utah, Ocean and Naru Islands in the Gilbert group, and in Egypt. The Rocky Mountain deposits have a comparatively low ranking in the phosphate trade of today, but this field contains one of the largest known reserves of phosphatic material, associated with which are recoverable trace minerals, which are of increasing importance in our national economy. The first discoveries of phosphate rock in the western states were recorded in Cache1 and Rich2 counties in Utah, respectively in 1889 and 1897. Mining operations were begun on these deposits near Montpelier, Idaho, in 1906. During the latter year geological studies of the phosphate beds were started by Weeks and Ferrier of the U. S. Geological Survey. These studies have been continued to the present day by a distinguished roster of the Survey's technicians. As a result of this systematic exploratory program, the Survey has published a series of bulletins, papers, and maps, which provide the mining public with a comprehensive study of the exposed

Jan 1, 1949

By WILLIAM BOWIE

IN most human endeavors a knowledge of the terrain is essential to the effective carrying out of projects, but no line of work is more dependent on maps than theoretical and applied geology. Maps of a kind do exist for all of the area of the United States, but most of them are crude affairs and of little use in engineering, planning, and scientific research. Topographic mapping in the United States was initiated on a national scale by the U. S. Geological Survey and the organizations that were merged in its creation to make base maps for geologists. Their work could not be effectively done then and cannot be effectively done now without maps that accurately delineate the earth's surface. The distribution of the rock masses that contain valuable mineral bodies, or that by their intrusion brought them into existence, is the first step in a study of the mineral resources of the nation. This work requires three-dimensional maps, that is, topographic maps on which the land forms are shown by contours.

Jan 1, 1938

By J. C. Uy, T. E. Davidson, A. P. Lee

The effects of hydrostatic pressures to 26 kbars on the micro structure of poly crystalline Cd, Zn, Bi, Sn, Zr, Mg, Cu, and Fe were examined. Pressure-induced microscopic plastic flow in the form of boundary migration, slip, multiple slip, or twinning has been observed either singly or in combination in cadmium, zinc, bismuth, and tin. No deformation was observed in zirconium, magnesium, copper, and iron. The occurrence of such deformation, in terms of its intensity and initiation pressure, relates directly to the degree of anisotropy in the linear compressibility. Pressure cycling does not significantly affect the residual tensile properties of a zinc alloy which exhibits pressure-induced deformation similar to that of Pure zinc. CLASSICAL elastic theory predicts that a superim-posed hydrostatic pressure will not induce shear stresses in an ideal material. Thus, in the case of homogeneous and isotropic materials plastic flow will not occur as a result of pressure exposure, regardless of the magnitude of the pressure, unless some form of phase transformation or permanent density change takes place. However, real materials, such as metals, often vary considerably from the condition of homogeneity and isotropy. For this reason, Vu and johannin' examined and observed hydrostatic pressure-induced microscopic deformation in polycrystalline cadmium and, zinc, but not in aluminum, to pressures of 9 kbars and indicated that its occurrence is related to anisotropy in the linear compressibility. In addition, Davidson and omaan' have reported pressure-induced deformation in polycrystalline bismuth below the 1-11 transformation pressure. It becomes apparent then that under certain conditions hydrostatic pressure can induce localized internal shear stresses in some metals of sufficient magnitude to cause plastic flow. In this work, eight pure single-phase metals of different lattice structures and degrees of elastic anisotropy were examined after pressure exposures of up to 26 kbars in order to establish the conditions under which such deformation occurs and the type of deformation as a function of pressure. The effects of pressure cycling on the mechanical proper-

Jan 1, 1965

Jan 1, 1967

By H. E. Elliott, R. S. Busk, A. T. Peters

One of the problems of the fabricator of metals and alloys is the propensity of some composition rarnges toward abnoermal grain growth during certain stages of fabrication. In this respect magnesium alloys are no exception among alloys. Fortunately, convenient foundry control methods have been developed by which the abnormal grain growth possible in certain magnesium-alloy castings can be suppressed. An unusual characteristic of magnesium alloys, however, is that castings of some composition ranges are subject to local grain growth during heat-treatment without the necessity of intentional mechanical stressing of the part prior to heat-treatment. This effect occurs only under certain critical casting conditions, and only in certain alloys of greater than about 8.5 per cent aluminum content, such as C alloy (Mg, 9 per cent A1, 2 Per cent Zn, 0.2 Per cent Mn) and G alloy (Mg, 10 per cent Al, 0.2 per cent Mn). The first observation of this phenomenon in cast magnesium alloys occasioned much surprise, since it is not observed in other meta1s- Jeffries and Archer1 have stated that "the grain size of cast metals, provided they have not been plastically deformed, cannot be changed by heating below the melting point." The study of the conditions leading to abnormal grain growth in cast magnesium alloys, and of the mechanism of this phenomenon, has led to some very interesting observations. Perhaps the most significant of these was the observation that stresses originating from cooling contraction in magnesium-alloy castings are the only stresses necessary, under certain conditions, to cause local recrystallization and subsequent grain growth in the casting during heat-treatment. Before recent developments, this phenomenon of abnormal local grain growth Was a definite problem in the production foundry on C alloy sand castings. Illustrated (Fig. I) is a picture of a casting scrapped because of this defect. A mottled effect is produced in coarse-grained areas by suitable etching solutions. The properties of metal in the affected area are much impaired by such grain coarsening. Ultimate tensile strengths of half the normal value have been measured in metal of this nature. In this paper are described the techniques that have been developed by The DOW Chemical Co. for studying, and in large measure solving, this production problem. Also discussed are studies of the mechanism by which excessive grain coarsening occurs, and the fundamental conditions that produce this effect. The abnormal grain growth discussed in this paper will be referred to as "germinasium since this term has been definedl as any process leading to an abnormally coarse grain size. This paper deals only with abnormal local grain growth that may occur during the solution heat-treatment of certain magnesium-alloy castings, as dis-

Jan 1, 1945

By J. C. Fisher

Nucleation theory is applied to martensite nucleation in substitutional iron alloys. Composition fluctuations are neglected, and a steady rate of nucleation is predicted for any composition and temperature. The maximum rate of nucleation (as a function of temperature) is shown to be measurable only for on extremely narrow composition range, being too great or too small outside this range. A number of experimental observations, including completely isothermal transformation in some alloys and composition-dependence of M. temperature in others, are compared with the calculated behavior. IN a previous report,¹ nucleation theory was applied to the formation of isothermal martensite in an Fe-Ni-Mn alloy. The experimental observations of Cech and Hollomon² were accounted for quantitatively. It now is of interest to examine the predictions of nucleation theory with respect to martensite transformation in substitutional iron alloys of other compositions. Since Fe-Ni alloys have received considerable attention, both as to their transformation kinetics and their free energies, they will be treated in detail, although the results apply with equal validity to other substitutional alloys. In substitutional alloys, where composition fluctuations can be neglected in volumes of critical nuclear size, the rate of nucleation of martensite in subcooled austenite is¹ n - Nv exp (—W*/kT) [I] where the free energy of formation of the critical size nucleus is W* = 8192 p (?² s³) [2] In the expressions for n and W*, the symbols have the following meanings: N is the number of atoms per unit volume; v, the atomic vibration frequency; 8, a function of the elastic constants of austenite and the shear angle of martensite; , the austenite/mar-tensite inter facial free energy; and ?fc is the free energy change per unit volume accompanying the transformation. Jones and Pumphrey² have determined the austenite to martensite free energy change as a function of nickel content and temperature for Fe-Ni alloys. Their expression is ?F = 2500 C + 1.25 (1 —C)?FFc cal per mol [3] where C is the atom fraction of nickel, and ?Ffe is the free energy change per unit volume for pure iron as tabulated by Zener4 (or, equivalently, Fisher"). From Eqs. 1 to 3, it is possible to calculate isothermal nucleation rates as a function of temperature and composition for Fe-Ni alloys. The only unknown parameter is (?² s³). The best value of this parameter for Fe-Ni alloys, determined from M. temperatures in a manner to be described shortly, is (?² s³)= 9.92 (10)21 cgs units [4] Taking this value of (?² s³), C-curves for isothermal nucleation were calculated for Fe-Ni alloys of several compositions, and are plotted in Fig. 1. It is evident from Fig. 1 that completely isothermal nucleation of martensite in Fe-Ni alloys can be observed experimentally for only a very narrow range of compositions. Cech and Hollomon find that a nucleation rate of about 10' nuclei per cc per sec is as fast as they can follow dilatometrically, and a rate of about 10-1 nucleus per cc per sec is about the slowest that can be measured conveniently. If the nucleation rate is to lie between the limits 10-1 10 the nickel content of an Fe-Ni alloy must fall in the atomic fraction range 0.299 5 C 5 0.302. Nickel contents lower than 0.299 correspond to nucleation rates too great to follow, and those higher than 0.302 to nucleation rates too slow to measure in a reasonable time.* In view of the narrow corn- position range in which successful isothermal measurements can be made, it is not surprising that only one substitutional alloy has been described' that comes close to being in the proper range.

Jan 1, 1954

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

By K. H. Heino

Two 200 T/da Lurgi Turbulent Layer fluid-bed roasters have been in operation at Canadian Electrolytic Zinc Limited since 1966. Zinc concentrate containing 52-54% Zn, 9-11% Fe,31-33% S is treated to produce calcine containing 60-62% Zn,10-12% Fe, .l-.3% S as sulphide and .8-1.2% S as sulphate. Each roaster train comprises a waste heat boiler, two cyclones in parallel and a two-field electrostatic precipitator. Distribution of calcine collected is 10-15 percent from bed overflow, 55-65 percent from boilers, 20-25 percent from cyclones and 2-6 percent from precipitators. A Monsanto designed contact plant produces acid at a rated capacity of 365 T/da (100% H2304 basis) from roaster gases diluted to 7.0-7.5% S02. The process steps are gas cleaning and cooling by weak acid scrubbing, acid mist removal in electrostatic precipitators, gas drying in 93.5-96.5% H2304, conversion of sulphur dioxide to sulphur trioxide in a four-pass converter containing vanadium pentoxide catalyst, and absorption of the sulphur trioxide in 98.1-98.3% H2S04. Product acid is 93.2% H2S04. Conversion efficiency is 97-98 percent and overall sulphur recovery from concentrate is 87-90 percent. The adjacent fertilizer plant has a capacity of 135 T/da of P205. The products are 54 percent phosphoric acid, run-of-pile triple superphosphate, and diammonium phosphate. The plant is of Ugine-Kuhlman design and consists of an air-cooled multiple tank reactor, a tilting pan filter, and a forced circultation vacuum evaporator. Triple superphosphate is made on a continuous belt and partially cured in a rotary dryer. Diammonium phosphate is produced by ammoniating phosphoric acid in a single stage reactor. The slurry of ammonium phosphate is granulated in a blunger and dried.

Jan 1, 1970

By Howard N. Eavenson

AN analysis of the bituminous coal situation by an authority who traces the production, mining, safety, markets and labor trends in comparison with other fuels. BEFORE 1918 the production of coal experienced a steady growth, with slight recessions in ouput in only twelve years (1837, 1841, 1852, 1855, 1861, 1874, 1876, 1889, 1894, 1905, 1909, 1914), and in each of these cases the loss was recovered in the following year and the increase continued. In each decade the output was doubled. Prices, while not high, allowed some profit. In 1918 during World War I, an output of 580 million tons was reached and with the exception of 1923 this total was not again reached until 1942, in World War 11. Losses of output in this period were much greater than ever before; in 1932 the total was 270 million tons less than in 1918 or 1923, and the loss after 1923 was not recovered until 1942. The greatest output was 631 million tons in 1947.

Jan 1, 1950

Jan 1, 1969