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By A. C. Watts

FOR several years, a mine in Colorado experienced considerable trouble from small fires caused by the blasting of coal. Although a well-known make of permissible powder was used, it was first thought that the powder ignited gas that might be present and that this, in turn, set fire to line brattices or to the coal. Experiments were, therefore, conducted with another make of powder, but the results convinced the superintendent of the mine, Robt. Williams, Jr., that the fires were not caused by the powder but by the high-voltage electric current used for detonating the shots. The mine "makes" gas very freely, giving off from three-fourths to a million cubic feet of methane per 24 hours. The coal is a good grade bituminous of a very free burning quality. Electric shot-firing from the outside after all men and animals were outside had been practiced for a number of years. The shooting circuit was connected with the main power circuit at the mouth of each entry. Shooting circuit switches were mounted in boxes, which were kept locked with the handle of the switch, in open position, showing through the bottom of the box. The door of the box could not be shut and locked when the shooting switch was closed. At the entrance to each room, or working place, a small switch, called the miner's switch, was placed on the shooting line. It was the duty of the miner, when entering his place at the beginning of the shift, to see that this switch was open and that it was kept open until he left the place at the end of the shift to go out of the mine. Grounded return was used for main power lines. The current was 500 volts, direct current, with 100 to 300 amp. The nearest working face was 9600 ft. from the shot-firers' switch outside the mine and the most remote working face was 2 ½ miles. The various working faces were scattered over a wide area between these two points.

Jan 9, 1925

By B. S. Norris, Charles R. Austin

The stresses which initiate deformation processes in metals are fundamentally important in the study of the mechanical properties of metals. A point of inflection in the load-elongation curves obtained for single crystals' has been rather too readily interpreted as a true yield point, and the critical resolved shearing stress on the plane of slip taken as a material constant. Even early work showed that the stress at this point varies with rate of loading, but it has not been generally appreciated that creep tests under static loads alone are suited for determining the existence or nonexistence of a yield point.* It has now been shown by Miller that single crystals of zinc3 when loaded statically begin to yield at loads too small to measure; as a result there is no case now known, apart from that cited in the present paper, in which a true critical stress for yielding has been demonstrated for single crystals of metals. The case of iron has especial interest: the existence of an upper and lower yield point and of an elongation at the yield point in ordinary iron and steel marks this substance as unusual, though the effects have been found to a very minor degree in other metals and alloys. $ Most alloys do not show such marked phenomena when appreciable yielding begins, and accordingly modern practice is to speak of the yield strength of such materials, a stress read from the load-elongation curve after elongation has begun, rather than yield point. The special behavior of iron suggests that it is more likely that single crystals of iron should have a true yield point than other metals. The study of the mechanical properties of metals and alloys requires a determination of the crystallographic mechanism of deformation, wlletller deformation proceeds by slip, twinning, or cleavage, or a combination of these, and a determination of the stresses that induce these modes of deformation. With this information, a study of the rates of work-

Jan 1, 1938

By Arthur H. Leigh

Anode mud, the residual material collected from the bottom of the electrolytic cells during the refining of copper is leached, roasted, fire-refined and cast into Dore1 metal anodes. Dore1 metal is a gold-silver-copper alloy containing 80 percent silver. The metal is processed electrolytically using the Moebius system to refine silver and separate gold, platinum and palladium. The Moebius cell cathodes receive a deposit of silver crystals which are melted and cast into 1000 ounce silver bars with 999 Fine minimum purity. Gold mud is collected in fabric bags and cast into gold anodes for further refining in the Wohlwill cells. Wohlwill cells are unique in that gold, the noble metal, can be put into solution electrolytically without the use of aqua regia. Gold is collected on high purity gold foil cathodes and cast into 400 ounce bull ion with 999.7 Fine minimum purity. Platinum and palladium remain in the electrolyte progressively increasing in concentration and are finally separated and purified by precipitation.

Jan 1, 1973

By T. S. Spicer

The relationship of coal characteristics to the principal types of firing equipment has been known to the coal combustion engineer, but is not as familiar a subject for purchasing agents, salesmen, consumers, and executives of coal-producing and consuming companies. This general survey of characteristics determined by standard laboratory tests, of major types of combustion techniques, and of the relationships between the two is directed toward the latter audience. It will also serve as a review for those actively engaged in the combustion of coal. Although the relationship of coal characteristics to the principal types of firing equipment is well known to the experienced coal combustion engineer, apparently there is need for a summary article on this subject. The author has received numerous requests for such a paper from purchasing agents, coal salesmen, coal customers and executives of coal-producing and consuming companies. Consequently, the scope of this paper will be directed to this audience, with the hope that it may serve also as a review to others actively engaged in the combustion of coal. The magnitude of this subject is so great that only a brief general treatise is possible. The author realizes that because there are so many special cases and exceptions to the generalities which follow, he is in jeopardy of contradicting himself. It is the hope, however, that the many references cited will prove valuable to those who wish to study the details excluded by necessity, due to space and time limitations. Hence, the characteristics of coals as determined by standard laboratory tests will be discussed; the major types of combustion techniques reviewed; and then the characteristics and firing will be related. CHARACTERISTICS OF UNITED STATES COALS The coals of the United States range from lignite to anthracite and each has its own general characteristics. The extensive coal fields of the U. S. are shown in Fig. 1 and the estimated reserve according to rank for each state is illustrated in Fig. 2. Coals may be classified according to rank as shown by Table I from the ASTM Standards on Coal and Coke, D-338-38.1 The basis of this classification is ac- cording to fixed carbon and heating value (Btu per pound) calculated to a mineral-matter-free basis. The high-rank coals are classified according to fixed carbon on the dry basis; and the low-rank coals according to Btu on the moist basis. Agglomerating and slacking (weathering) indices are used to differentiate between certain adjacent groups. While rank is not itself a characteristic it does signify certain characteristics that accompany a class of fuel. Anthracite, for example, immediately implies a hard, free-burning, smokeless coal of low volatile matter, usually having an ash of high fusibility. Coals may also be classified according to grade as described by ASTM Designation D-398-37.1 This quality classification is determined by size, calorific value, ash, ash-softening temperature, and sulfur. This type of classification is not used as extensively by the industry as the rank classification. Fig. 3 shows the heat value of different ranks compared to proximate analyses. Coals may also be classified by sizes, as shown in Tables IIA and IIB, and sizes can be on both top and bottom limits. If this is done, then the coal is called double screened; otherwise, either top or bottom sizes can be specified as a limit. Bituminous coal sizing varies from field to field and depends upon the market demand. The common sizes and their main uses are outlined in Table IIA. Anthracite is usually available in many sizes at the colliery, and Table IIB summarizes standard sizes and names. Although rank, grade, and size designations help identify and describe a coal in question, there still remain other characteristics such as indicated by moisture, free swelling index, grindability tests, etc. A bituminous coal information chart Table III) suggested for use in studying the available coals in a region, lists origin and chemical and physical characteristics. Even this more comprehensive list does not completely spell out all the characteristics of a heterogenous material like coal. For example,

Jan 1, 1961

By L. W. Casteel

This is a story of progress through research, invention and innovation-progress that made a small mine in Missouri into a large and prosperous corporation. The St. Joseph Lead Co. was founded in Borne Terre, Missouri, in 1864. At that time, the mine consisted of a narrow trench eight feet deep; the mill was a hand-operated jig; and the smelter, a charcoal oven with a sloping hearth. During the first year, production was suspended for two months because of an invasion by the Confederate army. There have been few interruptions since that time.

Jan 7, 1964

By J. R. Thompson

It is common practice, and certainly good business as all of us know, to take care of plant operating equipment. Machinery of any type requires periodic inspection and planned maintenance. With this thought in mind a plant operator should at the end of every shutdown period make regular belt inspections and plan for later appropriate care and maintenance. The points mentioned below are understood well by all of us but are sometimes forgotten because belt conveyors are comparatively easy to operate. Maintenance of any conveyor belt is dependent upon the fundamental characteristics of the two component parts-cover and carcass.

Jan 6, 1950

By Elbert Rowland

THE widespread interest in the alloys of beryllium with copper is due principally to the fact that certain compositions show very favorable precipitation-hardening characteristics and are, in fact, the strongest nonferrous alloys known at the present time. Investigations have been conducted by Masing and Dahl and others on the physical characteristics of ternary beryllium alloys, in an attempt to produce precipitation-hardening effects with a smaller amount of beryllium than that required in the binary copper-beryllium alloys (2.0 to 2.5 per cent Be). The results of these investigations show that ternary alloys of beryllium with Cu-Sn, Cu-Al and Cu-Zn, among others, exhibit promising improvements in physical properties after precipitation-hardening treatment and, while the increases in properties obtained are not as high as those realized from the binary copper-beryllium alloys, excellent properties are obtained with beryllium contents averaging about one-half the amount required in the binary alloys. This paper presents the results of an investigation of the equilibrium relations of certain alloys containing copper, tin and beryllium. The alpha-phase boundary of the ternary system is given for alloys containing from 0 to 1 per cent beryllium. The equilibrium conditions beyond the alpha-phase boundary are presented for alloys containing up to 32 per cent tin and 1 per cent beryllium. The data were collected by means of

Jan 1, 1935

By John McCaslin

ONE of the most common technical terms in the U. S. today is automation-a word not listed in the 1946 dictionary. The influence of automation on the national economy has been tremendous. It has even been the subject of congressional investigations. Automation, writes Aronson, substitutes mechanical, hydraulic, pneumatic, electric, and electronic devices for human effort and decision? Automatic devices and instruments are used extensively in some industries, but many others have yet to take full advantage of these great discoveries. The petroleum industry has been a leader in using automatic controls-some refineries are almost completely controlled by automatic devices. The field of geophysics is entirely dependent on instruments and has progressed at almost exactly the same rate as improvements in instrumentation. In metallurgy and mineral dressing use of instrumentation is increasing very rapidly. Mining engineers throughout the country are beginning to think in terms of instruments and controls.

Jan 3, 1958

By D. Watson, T. J. N. Grainger-Allan

A technique for studying the mechanism of the froth flotation process in which continuous froth removal does not take place but, instead, an equilibrium is reached between froth and pulp is described. A flotation cell, specially designed to facilitate equilibration, and froth and pulp sampling procedures are described. The main advantage of the technique is that the ability to measure the steady-state froth height allows froth-stability effects to be separated from pulp-process effects. In the flotation of hematite front quartz, linear relationships are found between airflow rate and froth height and between airflow rate and the ratio at equilibrium of mass of values in froth to mass of values in the pulp. A simple mechanistic interpretation of these results is given. It is suggested that froth-stability effects may play a more important role than hitherto allowed. In particular, the way in which concentration and size distribution of gangue particles may affect overall flotation rate is shown.

Jan 1, 1975

The Library of the above-named Societies is open from 9 A.M to 10 P. M. except on holidays. It contains about 70,000 volumes and 90,000 pamphlets, including sets of technical periodicals and publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library, through its Library Service Bureau, can render valuable service through correspondence; letters requesting information will receive especial attention. The Library is prepared to furnish references and photographic copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information on the geology and mineral resources of all countries. All communications should he made as definite as possible so that the information received may he what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape.

Jan 6, 1918

INTRODUCTION IT is 10. years this summer since the first of the contributions which it has been my privilege to make to the working tools of the hydrometallurgist was set at work, but a full description of what has come to be known as "Dorr Machinery" has never been published in the Transactions of the Institute, and it has been suggested to me that an account of the same would prove of interest to members, although most of those engaged in cyaniding and concentration are probably familiar with it. The account which I shall give of the development of the machines must be recognized as being written from the viewpoint mainly of my own local experience and not from that of one who was familiar with the general metallurgical practice throughout the world. Most advances in any art are conceived before the time is ripe for their development and any .invention which comes into general use will usually be found to have been tried out in a crude way and abandoned more than once. If the early experimenter went as far as the Patent Office, his work may serve no other purpose than to prevent the issuance of the broadest patent to those who later may develop a commercial process. The cyanide process in the United States early in 1904 was mainly confined to the leaching of dry crushed ores, both coarse and fine, and sand treatment of tailings from concentration and amalgamation. In the Black' hills some plants were crushing in cyanide solution, leaching sands and handling the slime by the well-known decantation process. Filter pressing, in use for some years in Australia,had been tried in several places in this country and the Moors process had been abandoned at Mercur after' a short run, but was doing good work at the mill of Lindbergh, Dorr & Wilson, at Terry, and being installed at Bodie and the Liberty Bell. A general feeling, however, still existed that, slimes were to be avoided when possible, on account of the losses in treatment and the difficulty of making a good leaching product when they were present in large amounts, especially when the crushing was done in cyanide solution.

Jan 8, 1914

By M. Lonoff

Byproducts are more important to the copper mining companies than to the copper market. Copper ores frequently contain gold, silver, molybdenum, lead, zinc, and cobalt. With the increase in the prices of these metals copper mining has become more profitable. If byproduct prices remain high, additional firms will be attracted to the copper industry; the increased supply of copper will reduce the long-run copper price. However, this is unlikely to happen because the markets for the copper byproducts, especially molybdenum and cobalt, are small. Increased recovery from copper and other sources will depress the prices of these byproducts before the copper price is significantly affected. Should byproduct prices remain high, the copper market will both settle at a lower long-run price and be more unstable in the short run. Since changes in the copper price do not affect the entire earnings of a multi-metal mine, the copper price must fall further before such mines reduce output in the short run. Higher byproduct revenues will make copper supply less responsive to copper prices; shifts in copper demand will result in greater copper price fluctuations in the short run than they did before.

Jan 1, 1984

By Eric Jette

THE alloys of gold and iron were investigated in 1907 by Isaac and Tammann,1 who determined the thermal diagram for the entire system by thermal analysis and microscopic examination. They also reviewed the previous literature. Since that time the present authors have been able to find only two additional references. Guertler and Schulze2 examined the electrical resistance of iron alloys containing up to 40 per cent by weight of gold between 0° and 200° C.; the alloys were in the form of wires. The main result of this work was to confirm the solid solubility limit found by Isaac and Tammann; namely, about 20 per cent Au. More recently, Shih3 has examined the magnetic properties of gold alloys containing up to 10 weight per cent iron and particularly the range below 5 per cent. The alloys in the lower range were found to be paramagnetic; the 10 per cent alloy was ferromagnetic. The present investigation was undertaken to determine the solid solubility limits at various temperatures, particularly below the a-y transformation point of iron, since these solubilities are of some impor-tance in connection with the working of the alloys in the manufacture of certain "grey" and "blue" golds.

Jan 1, 1934

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc. When Mr. Carnegie made his gift which made possible a home for the engineering societies, a separate corporation was organized to act as a holding company and to manage the common property. This was long known as the United Engineering Society, but the name has now been changed. to one which more nearly reflects the real function of the corporation. It holds title to the Engineering Societies Building and to various funds placed in its charge and is managed by a Board of Trustees, of which three are chosen by each of the four societies, American Institute of Mining and Metallurgical Engineers, American Society of Mechanical Engineers, American Institute of Electrical Engineers and American Society of Civil Engineers, which have equal and undivided interests in the property. The land and building cost two million dollars. During the gear 1934, the constitution and By-laws of The United Engineering Trustees, Inc., were thoroughly revised and a better organization of its functions was affected: The Engineering Foundation and the Engineering Societies Library were made "departments? of the United

Jan 1, 1936

A. L. FIELD, Cleveland, Ohio (written discussion*.-)In equation 2, B is used to denote the ratio of bases (lime plus magnesia ) to acids (alumina plus silica) it being stated that this ratio gives more concordant results than the ratio either of bases to silica, or of lime to silica. I find, however, that, by making use of the ratio between true CaO (CaO by analysis minus sulfur calculated to CaS) to acids, equation 2 may he modified to agree with the observed facts within an average error of 0.0041 per cent. sulfur instead of 0.0045 per cent. The revised equation is s = 0.072 + 0.01835 - 0.00061 (t - 1400) - 0.0403B where B is the ratio of true CaO to Al2O3 Plus Si02, and the other symbols have the same significance as before. I would not appear to stress too much this slightly better agreement of the revised equation with the observed sulfur. Yet I believe that the use of this ratio of true CaO to acids is to be preferred, if for no other reason than the fact that it is more in harmony with the previous findings of the Bureau of Mines with regard to the effect of magnesia and other impurities on slag viscosity.1

Jan 12, 1919

With the signing of the armistice on Nov. 11, the direction of the main concentration of effort of the United States was changed. In order to win the war, all industrial efforts had to be organized and centralized. With the war won and peace in sight, this centralization of effort stopped and the full play of individual initiative was allowed to resume its sway in the community. During this period of reversal of direction of effort, there was a natural loss of momentum and the United States, as well as the rest of the world, is in for a period of readjustment. The immense progress that was made in one direction under the stress of the necessities of war, which focused the energies of a nation in one direction, is an outstanding example of what can be accomplished if a community with many varying interests can be united on one objective which it desires to attain. The realization that the fusing of many interests into one stream of effort is difficult should not prevent us from taking the long view ahead that is necessary in order to be able to measure the progress made. If we don't have a mountain peak to guide us, we are very likely to run in circles in the plain without reaching the goal to which we strive. The most efficient development of natural resources is an ideal that, from a material point of view, appeals to the engineer. This ideal includes giving of opportunities to everyone to take a share in the development of these resources.. It also contemplates rewarding foresight

Jan 4, 1919

By E. Bicknese, R. Clark

The mechanism and rate of reduction of FeO at conditions similar to those in the stack of a blast furnace have been determined for temperatures from 980" to 1165°C. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal in a static system (no flow of reducing gas) have shown that the CO2-CO ratio of the product gas depends upon the relative reactivities of the Fe2O3 and charcoal. In a systern with a "hot blast" of CO and Nz (simitar to dry bosh gas), synthetic FeO, and actiuated coconut charcoal, the rate of reduction was not sensitive to the flow of reducing gas, and the rate-controlling step alas the chemical reaction at the metal-oxide interface. Wherz solid carbon was not present, a critical flow rate of reducing- gas had to be met in order to prevent a lowering of the reduction rate. The effect of a less-reactive carbon (blast-jurnace coke) and of a "natural" FeO on the mechanistn and rate, and the mininum amount of carbon necessary in the charge to tnaintain the reducing potential of the gas phase, have been determined. THE importance of iron oxide reduction processes has encouraged many studies of the process reaction kinetics. Despite this, the mechanism is not well-understood and three main theories have evolved, which can be stated as follows: A) the rate-controlling step is diffusion, either gaseous diffusion of the reductant or product gas through a porous solid,' or solid-state diffusion of iron and oxygen atoms through the so1id.2 B) The slow step is diffusion of reducing gas through a stagnant boundary layer. C) The reaction rate is controlled by the chemical reaction occurring at the metal-oxide interface and is proportional to the area of this interface.3 By increasing the velocity of the reducing gas to a flow rate beyond which no increase in the reduction rate is observed, critical flow rate, it may be possible to eliminate B as the slow step. However, as warnere points out, the establishment of a critical flow rate may only assure that the reaction is not limited by a reduction in the reducing potential of the gas and that B may still be the rate-determining step. Edstrom and Bitsianes and Seth and Ross8 show that A and C may both be correct for the reduction of the same oxide, depending upon the stage of the reduction, and that the relative importance of the two mechanisms varies with the porosity of the oxide. Themelis9 has derived expressions which express A, B, and C in terms of the fraction reduction, Rx, of a spherical particle. Thus, in the case of A a plot of In (1 - Rx) vs time must be linear and the time to reach a given reduction is proportional to the square of the particle diameter. For B a plot of (1 - Rx) vs must be linear and the time to reach a given reduction is proportional to the square of the diameter. For C a plot of 1 - (1 - RX)1/3 vs f must be linear and the time to reach a given degree of reduction should be proportional to the diameter. In the case of mixad controlled reactions, none of the plots are linear over their entire length. The results of previous studies, in which the rates of gaseous reduction of iron oxide were measured in the absence of carbon, may not correspond to blastfurnace practice because they ignore the effects of the Boudouard reaction. CO2 +C — 2CO The presence of carbon may alter the mechanism or the rate of iron oxide reduction through an enrichment of the gas phase by Eq. [1]. In this case, the presence of and reactivity of carbon become important. If the Boudouard reaction has no effect on the rate of reduction, the reducing gas could be supplied by some means other than the gasification of carbon at the tuyeres and carbon could, theoretically, be eliminated from the burden. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal were made to determine if the reactivity (surface area) of the Fe2O3 had any effect on the product gas composition. Two size fractions of Fe2O3 were reduced with charcoal in a static system (no flow of reducing gas). In each case the charcoal was -100 + 325 mesh and was 25 pct of the total charge. One fraction of the reagent-grade Fe2O3 was submicron in diameter. The other fraction was -100 + 200 mesh and was prepared from the former by compacting, sintering at 1300°C, crushing, and screening. In each experiment, the reaction vessel was filled with a mixture of CO and CO, which would be in equilibrium with FeO and iron at the reaction temperature. A furnace was heated to the desired temperature, the vessel was placed in the furnace, and the gaseous products of the reaction were collected and analyzed. The results of these experiments, Fig. 1, show that the gas phase associated with the submicron oxide is more oxidizing than that with the -100 + 200 mesh oxide. Therefore, in a static system, the relative rates of the reduction reaction and the gasification of carbon depend upon the reactivities of the Fe2O3 and charcoal. The reduction of FeO to iron is the most important reaction occurring in the blast furnace and is probably the slowest of the several reduction steps. The mechanism and rate of reduction of FeO in a system containing carbon and a flow of dry bosh gas have been studied. TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AlME

Jan 1, 1967

By E. J. Ripling

TUBES may be produced by a large number of forming processes, the most common of which will be discussed analytically in this paper. In no case will the stress analysis for any given tube producing process be derived formally for where such analyses are available, they may be referred to readily. Rather, emphasis will be placed on the interpretation of the theory of the different processes, few of which are developed to a state that will allow rigorous mathematical analyses, in an attempt to give a rational description of the effects of the different variables involved in each method. Tube producing methods can be divided into two groups: Those used to form shells, and those used to further work these shells into a shape more suitable for their final use. Among the first group are included roll piercing, extrusion and cupping for seamless shells, and bending with welding for welded tubes. The re-forming processes include sinking, drawing with a plug, and drawing with a rod. Only the plastic forming operations will be discussed here; other forming processes such as casting shells will not be considered. PRODUCTION OF SHELLS Shells for Seamless Tubing Piercing: The extremely important process of forming an axial hole in a billet by oblique rolling never has been analyzed satisfactorily, although a certain amount of experimental work relating to this process has been conducted. There are a number of factors that make piercing difficult to analyze; one of these is the fact that piercing is not a problem in plasticity, but one in fracturing, and the laws of fracturing are even less well understood than those of plasticity. If, however, it is assumed that fracturing occurs on a surface as a result of tensile stresses acting normal to this surface, piercing can be analyzed qualitatively by examining the stresses established in the oblique rolling process. To determine the origin of the tensile stresses that are thought to effect piercing, it will be necessary to know the angular relationships between the maximum stresses that are established in piercing. These angles quite frequently can be determined in a plastic deformation process by an examination of the deformed product. For example, consider the stresses established when a tensile test is conducted on a rectangular cross-sectional specimen of pearlitic steel. When stretched, this material first flows plastically, exhibiting the well-known yield jog on a stress-strain curve. The formation of the slip areas that give rise to the yield jog can be detected during the straining, since these flowed areas cause depressions on the specimen surfaces which can be seen if the surfaces are polished highly. The plastically strained areas also can be found after the specimen has been stretched to a strain not exceeding the yield jog, by sectioning the test piece and. etching these sections with Fry's etch. With this etchant, it is possible to dis-

Jan 1, 1951

By A. U. Seybolt

Experiments on both suljidation and hot corrosion have been carried out using ternary Ni-Cr-X alloys and commercial nickel-base superalloys. It has been shown that lhere are certain micro structural similarities between sulfidation using H,S/H2 mixtures and hot corvosion using Na,S04 in "crucible" experiments or hot corrosion tests using a flame tunnel apparatus. It is proposed that two key processes in the hot cowosion process are: 1) formation of chromium sulfides which deplete the alloy matrix, and 2) oxidation which can be accelerated because of chromium depletion. Other processes play an important role in the hot corrosion process, such as accelerated oxidation attack due to the presence of a N& S04 or N&SO,- NaC2 film which inhibits the formation of a protective external oxide scale. However, this latter phenomenon was not studied in this work. THE term hot corrosion has come to mean a combination of sulfur and oxygen attack on nickel-base or cobalt-base superalloys used as gas turbine blades or partitions. This attack can be initiated by any combustion process in air involving fuel containing sulfur if the sulfur level is sufficiently high. Levels of 5 pet SO2l for example, in the combusting gas have been observed to produce hot corrosion attack on nickel-base alloys. The important immediate corroding medium in aircraft gas turbines, however, has been established to be Na2S04, formed from reaction between NaCl from sea air and sulfur in the fuel.' The Na2S04 concentrates the sulfur sufficiently so that superalloy parts heated in the range 1400" to 1900°F can become sulfided by reducing the Na2S04 film which forms on the parts, and this reaction allows sulfur to gain access to the alloy. The sulfur thus released diffuses into the superalloy and forms primarily chromium sulfides of various compositions, but frequently Cr2S, has been identified. Figs. 1 and 2 show the morphology typical of hot corrosion of a cobalt-base superalloy X-45 (25 Cr, 10 Ni, 7.5 W, 0.25 C) and a nickel-base alloy, Udimet 500 (19 Cr, 19 Co, 4 Mo, 3 Ti, 2.9 Al, 0.07 C). Both alloy samples were subjected to the same hot corrosion conditions: 616 hr at 1600°F in a combusted 2.9 pct S distillate oil containing 125 ppm Na as NaC1. It will be noted at once that the nickel-base alloy is much more severely attacked. The depth of corrosion is much greater and the number and size of the sulfides present are much greater. Both alloys show a duplex oxide scale, which is more noticeable in the X-45 alloy. The external scale is probably a spinel in both cases, with CrQ3 lying next to the alloy. Many investigators1 -"ve been concerned with hot corrosion phenomena, but there has been a lack of unanimity of opinion as to the details of the hot corrosion mechanism. More than one definition of hot corrosion is possible. Some investigators con- sider as a measure of hot corrosion only the weight gain due to an accelerated oxidation. However another point of view is that the total depth of affected alloy may be used as a measure. While it is recognized that surface oxidation attack is greatly accelerated by the presence of salts like Na2S04 or Na2S04-NaC1 mixtures, sulfur penetration into the alloy also undoubtedly produces very important effects. The region of sul-fide penetration which is so prominent in Fig. 2 is one of the outstanding characteristics of hot corrosion. For highly stressed parts, such as first-stage buckets, this sulfur-penetrated region can be more significant in mechanical property loss than the reduction of cross section produced by the formation of the massive external scale. In addition, evidence will be presented that this sulfided region can be less resistant to subsequent oxidation attack. Since it appears that the sulfided region below the surface oxide scale plays an important role in the overall corrosion process,

Jan 1, 1969

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale formation) in alloys of silver with 2, 7 5, and 30 per cent of copper The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver' Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail 5,6 The present research confirms this anticipation The oxidation of a series of 20 dilute alloys of silver has been studied metallographically, some types of subscale not encountered among the copper alloys have been found Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation, i e , they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found The probable reasons for this difference in behavior will be discussed presently EXPERIMENTAL PROCEDURE Silver -The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99 993 per cent Ag)* and the purest avail-

Jan 1, 1942