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By C. H. Mathewson

MY treatment of the subject of "Metals of the Future" is imaginative rather than statistical or scientific, because reliable information concerning useful concentrations in the form of ore deposits of by far the majority of the elements does not exist and the chemical, physical, and mechanical properties of the unfamiliar metals are recorded only in fragmentary and uncertain form or not at all.

Jan 1, 1944

By Earnshaw Cook, H. S. Avery, J. A. Fellows

TEe increased use of heat-resistant alloys (26 per cent Cr, 12 per cent Ni; 16 per cent Cr, 35 per cent Ni; 12 per cent Cr, 60 per cent Ni; etc.) in recent years has been accompanied by continued demands by the consumer for improvement in properties. The manufacturers of these materials, of necessity, have resorted to more critical studies of the basic causes of variations in fundamental properties. To keep pace with the need for augmented information, previous techniques of investigation have been refined and new test methods and instruments created. It is the purpose of this paper to describe the apparatus, experimental technique and precision of measurement that were employed in the exploration of properties of heat-resistant alloys presented in a companion paper. The detailed precautions in experimental procedure essential for attainment of accurate and comparable data at elevated temperatures cannot be too highly emphasized. The Creep Test Since the fundamental concepts of creep testing have been recognized for the past 20 years, present interest is restricted to refinements in equipment and experimental procedure. The creep-test iaboratory constructed for the American Brake Shoe and Foundry Co. is designed to permit I000-hr. tests in the temperature range of I200° to 2 200°F. with a choice of applied stress extending from jo to 50,000 lb. per sq. in. in increments of 50 lb. per sq. in. To simplify the calculation of weight combinations, the loading beams (Fig. I) are provided with counterweights to eliminate the tare. The precision of the knife-edges (10:I ratio) is such that a 10-gram weight placed on the upper specimen grip will be exactly balanced by a I-gram weight attached to the loading shackle. Check of the loading weights proved the maximum error to be 0.06 per cent. Axial alignment is provided by crossed knife-edges in the grip seats. The furnaces are similar in design to those of Crane and Company, Battelle Memorial Institute, and the U.S. Steel Corporation. An 80 per cent Pt, zo per cent Rh No. 19 B. and S. gauge wire is used as the heating element. The details of -construction are shown in the radiograph reproduced in Fig. 2. The windings are held in place on an alundum tube with aludum cement; the distribution of turns is adjusted to give a maximum temperature gradient of , I°F. over a 4-in. gauge length (Fig. 3). To avoid sharp temperature differentials at the ends of the test section, the length of the furnace is four times the gauge length. Sixteen-inch coupons are used „ to reduce the temperature of the threaded joints and thus to facilitate removal from the grips. Thermal losses are minimized by refractory insulators cut to shape and surrounded by diatomaceous ear,th. The taps

Jan 1, 1942

By J. A. Fellows, Earnshaw Cook, H. S. Avery

TEe increased use of heat-resistant alloys (26 per cent Cr, 12 per cent Ni; 16 per cent Cr, 35 per cent Ni; 12 per cent Cr, 60 per cent Ni; etc.) in recent years has been accompanied by continued demands by the consumer for improvement in properties. The manufacturers of these materials, of necessity, have resorted to more critical studies of the basic causes of variations in fundamental properties. To keep pace with the need for augmented information, previous techniques of investigation have been refined and new test methods and instruments created. It is the purpose of this paper to describe the apparatus, experimental technique and precision of measurement that were employed in the exploration of properties of heat-resistant alloys presented in a companion paper. The detailed precautions in experimental procedure essential for attainment of accurate and comparable data at elevated temperatures cannot be too highly emphasized. The Creep Test Since the fundamental concepts of creep testing have been recognized for the past 20 years, present interest is restricted to refinements in equipment and experimental procedure. The creep-test iaboratory constructed for the American Brake Shoe and Foundry Co. is designed to permit I000-hr. tests in the temperature range of I200° to 2 200°F. with a choice of applied stress extending from jo to 50,000 lb. per sq. in. in increments of 50 lb. per sq. in. To simplify the calculation of weight combinations, the loading beams (Fig. I) are provided with counterweights to eliminate the tare. The precision of the knife-edges (10:I ratio) is such that a 10-gram weight placed on the upper specimen grip will be exactly balanced by a I-gram weight attached to the loading shackle. Check of the loading weights proved the maximum error to be 0.06 per cent. Axial alignment is provided by crossed knife-edges in the grip seats. The furnaces are similar in design to those of Crane and Company, Battelle Memorial Institute, and the U.S. Steel Corporation. An 80 per cent Pt, zo per cent Rh No. 19 B. and S. gauge wire is used as the heating element. The details of -construction are shown in the radiograph reproduced in Fig. 2. The windings are held in place on an alundum tube with aludum cement; the distribution of turns is adjusted to give a maximum temperature gradient of , I°F. over a 4-in. gauge length (Fig. 3). To avoid sharp temperature differentials at the ends of the test section, the length of the furnace is four times the gauge length. Sixteen-inch coupons are used „ to reduce the temperature of the threaded joints and thus to facilitate removal from the grips. Thermal losses are minimized by refractory insulators cut to shape and surrounded by diatomaceous ear,th. The taps

Jan 1, 1942

By F. C. Foshag, P. E. Wingrove

The Kayford, Boone and Nicholas Division of Bethlehem Mines Corp. operates a modern coal preparation plant in Van, WV. Since start-up of the Van plant in 1976 until the summer of 1980, the refuse handling system proved to be a costly maintenance problem and a material handling bottleneck. During the 1980 two-week miners' vacation, the original system - which included two screw conveyors and a drag conveyor - was replaced by an installation using two Flexowall steep angle belt conveyors. This paper describes the technical and economic analysis that led to the new installation and reviews its first year operating performance.

Jan 1, 1983

By Cyril Stanley Smith

ARCHEOLOGISTS, by use of the terms Bronze Age and Iron Age, indicate that metals have in the past determined the character of civilization. The relatively simple discovery by a primitive metallurgist that the addition of tin to copper both facilitated the production of castings and increased the durability of the product enabled hunter, warrior, and housewife alike to do things never dreamed of before. Similarly, the smelting of iron and the discovery of hardening methods greatly changed the arts of peace and war. Discoveries of low-melting-point alloys for joining and for making household utensils, and perhaps the adornment of a feminine form by sparkling precious-metal jewelry, have at times changed the destiny of a country. Bronze cannon, the cast and wrought iron Watt engine, copper transmission lines, and aluminum alloy aircraft, are cases of particular metals making possible the realization of an improved engineering design. Perhaps of the greatest influence of all upon civilization was the development of type metal. The rapid increase in the rate of dissemination of knowledge dates from the day that the technique of the pewterer was utilized in making rapidly reproducible and accurately sized letters for printing. It was not movable type, but metal type that was important, for metal castings could be made of identically the same shape and size at an enormous rate, and possessed excellent inking and wearing characteristics.

Jan 1, 1946

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Jan 1, 1938

William R. Walker, assistant to the president of the U. S. Steel Corpn., died at St. Luke's Hospital, New York, on Dec. 20, 1922. He was born at LaPort, Ind., Nov. 26, 1857, and his whole career has been closely identified with the iron and steel industry. His first employment was with the North Chicago Rolling Mill Co., Chicago; then he was appointed chemist for the Crown Point Iron Co., at Crown Point, N. Y.; and later he was works superintendent for Spang, Chalfant & Co., of Pittsburgh. He was early associated with Robert Forsyth, the well-known engineer who constructed the South Chicago works of the North Chicago Rolling Mill Company. Prior to 1890, Mr. Walker was works manager for the Union Steel Co., and upon organization of the Illinois Steel Co. he became general manager of its South Chicago works. At the time of the formation of the U. S. Steel Corpn., in 1901, he was appointed assistant to the president, which position he held until the time of his death. Through the technical staffs and committees of the Steel Corpora tion, Mr. Walker had an excellent opportunity to study and direct the development of mechanical methods for coal mining, coal washing, beehive coking, including the collection and recovery of its byproducts, and to interest himself in byproduct coke ovens, and the design and operation of processes for the coking of special coal mixtures. He also brought his experience to bear on the design, construction and operation of the blast furnace and its appurtenances, as well as the bessemer, open-hearth and electric steel processes. Incidentally, he was interested in microscopy and metallography, and was familiar with the manufacture of products related to the iron and steel industry, such as tin, zinc, sulfuric acid and many other substances. Mr. Walker had the remarkable faculty of being able to discuss and conduct investigations in practically any technical branch of the ferrous industry. In the words of President James A. Farrell, "Mr. Wdker was a man of keen mental attainments and possessed an exceptional knowledge of the iron and steel industry, from both the scientific and the practical

Jan 1, 1923

William R. Walker, assistant to the president of the U. S. Steel Corpn., died at St. Luke's Hospital, New York, on Dec. 20, 1922. He was born at LaPort, Ind., Nov. 26, 1857, and his whole career has been closely identified with the iron and steel industry. His first employment was with the North Chicago Rolling Mill Co., Chicago; then he was appointed chemist for the Crown Point Iron Co., at Crown Point, N. Y.; and later he was works superintendent for Spang, Chalfant & Co., of Pittsburgh. He was early associated with Robert Forsyth, the well-known engineer who constructed the South Chicago works of the North Chicago Rolling Mill Company. Prior to 1890, Mr. Walker was works manager for the Union Steel Co., and upon organization of the Illinois Steel Co. he became general manager of its South Chicago works. At the time of the formation of the U. S. Steel Corpn., in 1901, he was appointed assistant to the president, which position he held until the time of his death. Through the technical staffs and committees of the Steel Corpora tion, Mr. Walker had an excellent opportunity to study and direct the development of mechanical methods for coal mining, coal washing, beehive coking, including the collection and recovery of its byproducts, and to interest himself in byproduct coke ovens, and the design and operation of processes for the coking of special coal mixtures. He also brought his experience to bear on the design, construction and operation of the blast furnace and its appurtenances, as well as the bessemer, open-hearth and electric steel processes. Incidentally, he was interested in microscopy and metallography, and was familiar with the manufacture of products related to the iron and steel industry, such as tin, zinc, sulfuric acid and many other substances. Mr. Walker had the remarkable faculty of being able to discuss and conduct investigations in practically any technical branch of the ferrous industry. In the words of President James A. Farrell, "Mr. Wdker was a man of keen mental attainments and possessed an exceptional knowledge of the iron and steel industry, from both the scientific and the practical

Jan 1, 1923

By A. J. Stosick, J. R. Hoffman, E. Rudy, St. Windisch

The binary alloy system Mo-C zoas investigated by means of X-ray, metallog/aphic, thermoanalytical, and melting-point techniques on chemically analyzed specimens. The system, Fig. 39, is characterized by three congruently melting, intermediate phases, Mo2C, n MoCi-x, and aMoC1-,, of which only Mo,C is stable at temperatures below 1650°C. Substoichio-metrzc (~32.5 at. pct C) dimolybdenum carbide undergoes a homogeneous sublattice order-disorder transformation at temperatures of approximately 1400°C, whereas hyperstoichiorrletric compositions undergo a discontinuous Phase change. The order-disorder transitions in the Me, C phases are discussed in terms of the structural changes involved in the transformation processes and the absence of long-range sublattice coherency in stoichiometric or hyperstoiclziomet-ric compositions attributed to the impossibility of obtaining long-range order in a linear chain of alternating carbon atoms and vacancies. From the experimental phase relutionships and the known thermody-namic data for Mo2 C, limits for the free energies of formation for the high-temperature phases r) MoC1-, and aMoC1-, are deriued and found to be in good agreement with data previously obtained from phase equilibria in ternary metal-carbon systems. IN the course of studies of the high-temperature phase relationships in ternary systems of refractory transition metals with carbon,' a number of inconsistencies found in previous work necessitated a reex-amination of some of the related metal-carbon binaries. A reassessment of the binary system data also seemed

Jan 1, 1968

By Maurice E. Peloubet

This discussion of accounting will describe the statements and the information that the accounting system produces, from the point of view of those who use such systems rather than of those who prepare them and who do the detail and technical accounting work. In any well organized mine, quarry, or other enterprise exploiting a mineral deposit, no matter how small, some clerical and accounting work must be done. Miners and other employes must be paid, supplies must be purchased and issued, and various tax and information returns, which even the smallest enterprise must file, have to be prepared. In this chapter it is assumed that the enterprise has employes of this type and that they understand the fundamentals of record keeping and accounting. It would be impossible here to give sufficiently full explanations to enable a man with no previous clerical and accounting training to set up and operate an accounting and cost system for even the simplest extractive operation. Rather, we shall hope first, to tell the investor and the operator, from the chief engineer or president down to a subforeman, what to expect from the accounting statements and records and how to use this information in his daily work; and second, that it will enable the man with some knowledge of accounting or book- keeping, but with little or no experience in any extractive industry, to set up and operate a satisfactory system for a mine or other extractive enterprise. For readers who wish to go further, the bibliography at the end of this chapter contains many references. T he emphasis has, therefore, been placed on the statements to be produced and the purposes for which they are to be used rather than the underlying books and records. These are, with a few exceptions which will be described later, essentially what might be found in any industrial enterprise and would probably, in the extremely small enterprise, consist of handwritten journals, ledgers, analysis books, payroll books, and stores ledgers. In the larger enterprise, various types of mechanical accounting would be introduced in proportion to the complexity of the operation.

Jan 1, 1964

Remarks of Mr. Robert W. Hunt, General, Superintendent, Albany and Rensselaer Iron and Steel Company., Troy N. Y.—In discussing Dr. Dudley's two most interesting papers, I feel a natural hesitancy in disagreeing with conclusions formed after such careful and conscientious work. But I think he has made his deductions from too meagre premises. The analyses of but twenty-five samples are entirely too few to justify the establishment of so important a formula. When we consider that he indirectly proposes to regulate an interest amounting, even at the present low prices, to over $20,000,000 per annum, we may well hesitate before accepting a formula based upon the chemical and physical analyses of but twenty-five steel rails. Dr. Dudley touches the keynote in referring to the proposed labors of the Government Test Commission. They based their hopes of attaining success upon the chemical and physical analyses of a very large number of samples, and in the only branch of investigation which the short-sighted policy of Congress has allowed them to complete, i.e., chain cables, we find that a dozen, twenty-five or one hundred tests gave no satisfactory results. It was only after many hundreds that they were enabled to' draw conclusions. There are so many circumstances hearing upon the life of a rail, that the task of extracting a correct result seems herculean. I presume I am right in stating that in our Northern latitudes early winter and spring months witness the breaking of the greatest number of rails, thus seeming to prove that an unstable road-bed has much to answer for. Then, again, broken and flattened wheels must be taken into account, but I am convinced that more rails have been broken by the treatment which they received before leaving the rolling-mill

Jan 1, 1879

Remarks Of Mr. Robert W. Hunt, General Superintendent, Albany And Rensselaer Iron And Steel Company., Troy N. Y. - In discussing Dr. Dudley's two most interesting papers, I feel a natural hesitancy in disagreeing with conclusions formed after such careful and conscientious work. But I think he has made his deductions from too meagre premises. The analyses of but twenty-five samples are entirely too few to justify the establishment of so important a formula. When we consider that he indirectly proposes to regulate an interest amounting, even at the present low prices, to over $20,000,000 per annum, we may well hesitate before accepting a formula based upon the chemical and physical analyses of but twenty-five steel rails. Dr. Dudley touches the keynote in referring to the proposed labors of the Government Test Commission. They based their hopes of attaining success upon the chemical and physical analyses of a very large number of samples, and in the only branch of investigation which the short-sighted policy of Congress has allowed them to complete, i.e., chain cables, we find that a dozen, twenty-five or one hundred tests gave no satisfactory results. It was only after many hundreds that they were enabled to draw conclusions. There are so many circumstances bearing upon the life of a rail, that the task of extracting a correct result seems herculean. I presume I am right in stating that in our Northern latitudes early winter and spring months witness the breaking of the greatest number of rails, thus seeming to prove that an unstable road-bed has much to answer for. Then, again, broken and flattened wheels must be taken into account, but I am convinced that more rails have been broken by the treatment which they received before leaving the rolling-mill * The remarks of the participants in this debate have been written out by the speakers, and are here given without any attempt to retain the order of the dis¬cussion. While the report does not, therefore, preserve the vigor and spontaneity of the debate, it is believed that it gains in value by giving the matured views of the speakers. The continuation of this discussion at the Pittsburgh Meeting, May, 1879 (beginning with remarks of Mr. Cloud on page 401), is appended for convenience of reference.-T. M. D., Sec'y

Jan 1, 1879

By Cadwallader Evans

MY endeavor in this paper will be to tell something of the accomplishments and current problems of the anthracite producer and to suggest some of the avenues for technical development that seem to me to be the most necessary and likely to bear fruitful results. The several subjects, that I find of most interest will be taken up individually with brief reference to the future trend. Underground Mining and Loading ?In this field great progress has been made in the last twenty years, beginning with the introduction of the scraper system. The electrical hoists for the operation of scrapers have been improved, and give little trouble, but there is an open field for the improvement of the auxiliary apparatus, particularly in the application of roller-hearing sheaves to the guiding of scraper ropes. Also notable in the last six or seven years is the introduction of shaker chutes, so that far more anthracite is now loaded over them than by scrapers. This trend should continue to be manifest, particularly if those who are looking ahead and who are charged with the development of this specialty continue constantly to study and improve the mechanical design of their shakers.

Jan 1, 1938

By A. Lucian Walker

SILVER is not only of paramount importance to millions of people as a medium of savings and to other millions as a medium of exchange, but it is also valuable and useful in industry. Mexico continues to be the largest producer of this metal, followed by the United States, Canada, and Peru. The largest consumers are China and India, which normally absorb about two-thirds of the world's mine production, hoarding it as savings. The imports by these countries exert a powerful influence upon the price, yet neither country is on the silver standard. China having abandoned it in 1935 and India in 1893, when the rupee was definitely linked to the pound sterling. Other nations such as Persia, Ethiopia, Mexico, and many of the South American countries either have been on the silver standard or have used silver as their chief circulating medium, and most large nations use it for subsidiary coins, this use accounting for 20 to 30 million ounces annually. The arts and industries have consumed 35 to 40 million ounces each year.

Jan 1, 1937

Jan 1, 1915

By Nathaniel Arbiter

There is a history in all men's lives, Figuring the nature of the times deceas'd, The which observ'd, a man may prophesy, With a near aim, of the main chance of things. W. Shakespeare, Henry IV; Part 2 Introduction This nation's first century embraced two stages of the Industrial Revolution. During one, what had been a colonial agricultural economy began to industrialize; water power, then steam after 1794, were the energy sources; coal and iron were the essential ingredients. The second stage started after 1850; aided by rich and diverse mineral resources, the country began its transition from the Iron Age to the Age of Metals. Early civilizations had been built on stone, and fairly high levels were sustained on iron. But the spectacular advances in the past century in communication, in construction, in transportation by sea, rail, land and air, and in much that characterizes modern civilization have depended increasingly on the use of the complete metallic and nonmetallic resources of the earth's crust. Thus it was appropriate to define the Industrial Revolution as “the period during which man's relationship to natural resources became utterly changed”, 1 with minerals playing a major and indispensable role. But we are now becoming aware that the relationship of man to natural resources must change again. On every hand the dangers inherent in the contamination of land, sea and air by the wastes of civilization are becoming apparent. And from the growing realization that mineral wealth is finite must eventually come other far reaching changes in mineral use and distribution. For on the scale of centuries we cannot continue to exploit mineral resources even at present rates, let alone at expanded rates, without eventual depletion of the more abundant resources, and early exhaustion of the less abundant. In the past our problems were relatively easily met by the development of new and improved machinery and processes. But the future will

Jan 1, 1971

By R. M. Howe, J. Spotts McDowell

Preparation and Use.—Magnesite is an important refractory in open-hearth, heating, and electric furnaces for steel-making and in many of those employed in the metallurgy of copper and lead. It is sold in the form of brick, finely ground "furnace magnesite" for bricklaying, and dead-burned grains for making and repairing furnace bottoms. The latter are a mixture of granules varying in size from pieces of about 5/8 in. (1.6 cm.) diameter to very fine but sandy particles. Dead-burned magnesite results from calcining the crude or lightly burned mineral at a temperaturc that will not merely drive off practically all the CO2, but will also cause sintering of the particles. During this process the pieces shrink considerably and become hard, dense, and inert to atmospheric moisture and CO2; under-burned material, on the other hand, will hydrate on exposure to the air. A small percentage of ferric oxide seems to be necessary for the production of a satisfactory sinter; from 4.5 to 8 per cent. in the dead-burned grains is considered the most desirable amount. Dolomite has been little used for brickmaking in the United States, but it is prepared for use in the granular condition calcined or "double-burned" and is the principal ingredient of several materials offered for sale under various trade names for refractory purposes. Dolomitic refractories are almost wholly confined to the open-hearth and electric furnaces, where they are used for fettling and as substitutes for magnesite. Much more magnesite and dolomite are used for basic open-hearth steel-making than for all other refractory purposes. The hearth of the furnace is usually built up of magnesite brick and dead-burned grain magnesite so laid that the brick base is protected by a working bottom of the granular material. The latter is sintered into place in layers 1/2 to 1 in: (1.25 to 2.5 cm.) thick to a total depth of 12 to 18 in. (30 to 45 cm.) at the center of the furnace. After each heat, burned dolomite is thrown against the banks as high as it will stick, and all holes in the bottom are Glled. At most plants such holes, at the end of each week, are also carefully filled with dead-burned grain magnesite. For temporary

Jan 1, 1920

By Frederick Laist

This paper is a review of Montana reverberatory smelting practice covering a period of approximately fifty years, during which time the small furnaces that had been in use elsewhere for a century or more, without much change in size or method of operation, were revolutionized and were developed into the huge, continuously operating furnaces of today. A study of Montana practice is particularly instructive, since reverberatory furnace smelting for the production of copper matte received more attention there than in other smelting centers and many of the improvements that finally resulted in establishing the preeminence of this type of furnace over the blast furnace originated in Butte and Anaconda. The material in this paper was gathered from original sources, wherever possible, and all of the illustrations were made from original drawings, some of which have been simplified and worked over so as to be better adapted for reproduction. The aim has been to trace the modifications in design and operation which took place during the period in question—the reasons for the changes and the results achieved through them. For developments during the first twenty years, the technical literature of the period was freely drawn upon, but I am particularly indebted to W. M. Kelly, general foreman at the Anaconda Works, whose recollections and personal experience extend back to the early days. I wish to acknowledge the use made of publications of E. P. Mathewson, William Wraith and L. V. Bender, as well as information obtained here and there from friends and associates. The resume of Great Falls practice was compiled from correspondence, notes and drawings found in the files of the old Boston & Montana Co. and the tabulations showing the performance of furnaces at Butte and Anaconda are adapted from plant records and correspondence in the files of the Anaconda Copper Mining Company. The paper deals with some interesting comparisons that were made between furnaces operated under various conditions in connection with the Carson Case, and results obtained when using natural gas as fuel. This part of the paper may be considered original to the extent that these results have not previously been published.

Jan 1, 1934

By C. A. Heiland

For a long time it has been known that it is possible to deduce conclusions about the physical constitution of the interior of the earth from the records of natural earthquakes obtained by stationary seismographs. In view of this fact it is surprising how late, relatively speaking, geologic prospecting by seismic methods has been taken up, although the first suggestion was made 40 years ago- that travel-time curves of artificial explosions might be used for the study of the change of the velocity of seismic waves as depth. Further suggestions of practical applications of artificial explosions for geologic purposes were made by Belar,2 by von dem Borne,3 by Benndorf4 and by Galitzin,5 but it was not until 1919 that Mintrop obtained. a patent on the seismic prospecting method which he has applied commercially on a large scale ever since. Dr. Mintrop came to this country with his method at about 1923. Since that time, several. American oil companies have developed seismographs of the mechanical type for the vertical component similar to that of Mintrop's (Humble Oil Co., Dr. Ricker). Other consulting geophysical companies designed other types of seismic devices, the simplest of them for the recording of the first impulse being the geophone (McCollum Geophone Co.). The galvanometric recording method as first proposed by Galitzin is being used (Geophysical Research Corpn.?) and use is being made even of the piezoelectric properties of crystals for portable seismographs (F. Rieber).. There is such an enormous variety of all kinds of portable seismographs, vibrographs, accelerographs, etc., that it is difficult to decide just what kind is preferable. Unfortunately, nothing has been published as yet about American designs of portable seismographs, except the Wood Anderson torsion-seismometer. After Mintrop's design of portable seismographs, other constructions were made.

Jan 1, 1928

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969