Search Documents

By Leon McCulloch

WIIen clean iron and metallic zinc dust, protected from the air, arc heated below the melting point of zinc, the iron takes on a coating that has excellent protective value. This coating is a brittle alloy of zinc and iron, and the process is called sherardizing. Although the zinc particlcs are covered with oxide and cannot touch the iron, an extremcly small amount of the zinc vaporizes and the vapor, reaching the iron, alloys with it. Other zinc then vaporizes to replace that which has been removed from the atmosphere. This process continues indefinitely at a decreasing rate, for the coating already formed permits zinc to diffuse through it to combine with the iron beneath. In this way, the coating grows outward from the surface of the iron, as the bark grows from a tree. The method of growth was clcarly seen while sherardizing small cubes of cast iron, at about 450" C., in a srnall glass-stoppcrcd bottle enclosed in a rotating drum. The dust contained about 3 per cent. iron, which prevented caking, and coatings % in. thick were grown in a few hours. After a heavy layer had been formed, the cubes mere again treated for a shorter time. The layer last formed was seen to lie next to the iron, instead of at the outer surface, showing that the growth was from the surface of the iron outward. The coatings split at the edges and corners, leaving the iron exposed there. Flakes of graphite from the iron were lifted upward and embedded in the coatings. The composition of sherardized coatings varies from the outer surface inward, as would be expected from the mode of growth. That is, the iron content increases slowly at first, then more rapidly as the iron is approached. At the surface the least amount of iron possible is 6 per cent., as the experiments described below have shown. A study was made of the effect of iron in zinc dust on the proccss and on the resulting coatings. Glass bulbs, holding the small pieces to be sherardized, together with enough zinc dust to make them two-thirds full, were heated in a small, rotating electrically heated and controlled furnacc. The bulbs had 6-in. (15 cm.) necks, of 96-in. (9.Fj mm.) tubing, plugged

Jan 1, 1923

By W. T. Lankford, Low J. R., Gensamer M.

The problem of sheet metal formability is one which has received a vast amount of attention during recent years. In spite of the great amount of study and experimental work which has been devoted to this problem, many of its fundamental aspects are still not well understood. No generally satisfactory test has been developed which is capable of providing a reasonably adequate evaluation of sheet metal formability, particularly in borderline cases. Anomalies persistently arise in which a lot of supposedly satisfactory material exhibits excessive breakage when formed. This lack of suitable technological tests greatly hinders the design of new parts and the substitution of new materials in parts of existing design, frequently necessitating considerable costly trial and error experimentation on an actual production basis. When, at the beginning of World War 11, it became apparent that mass production methods of forming would bc required in the aircraft industry if the large numbers of military aircraft needed were to be supplied, renewed attention was focussed on the problem of sheet metal formability. It was widely recognized that the formability requirements placed on sheet metals had been steadily increasing in severity through the years, especially as greater and greater emphasis was placed on streamlined designs with the resultant freer application of doubly curved surfaces. The recent advent of several new high strength aluminum alloys of more limited formability than some of the older alloys also served to emphasize the need for new approaches to the problem. It seemed evident that progress in the technology of sheet metal forming would depend to a great extent on the development of more reliable criteria for the evaluation of formability. Although the problem is admittedly very complex, the most logical approach appeared to be through studies of the fundamental material properties of sheet metals, especially under complex stress conditions simulating those prevailing in actual forming operations. Most previous investigations have failed to make full use of existing knowledge of fundamental material properties, and in many instances have attempted correlations with properties which are now recognized as being ambiguous in nature. This investigation was undertaken, therefore, with the aim of developing methods for the study of the flow and fracture of sheet meta1s under combined stresses, and of making use of such methods as might be developed in

Jan 1, 1947

By Low J. R., Gensamer M., W. T. Lankford

The problem of sheet metal formability is one which has received a vast amount of attention during recent years. In spite of the great amount of study and experimental work which has been devoted to this problem, many of its fundamental aspects are still not well understood. No generally satisfactory test has been developed which is capable of providing a reasonably adequate evaluation of sheet metal formability, particularly in borderline cases. Anomalies persistently arise in which a lot of supposedly satisfactory material exhibits excessive breakage when formed. This lack of suitable technological tests greatly hinders the design of new parts and the substitution of new materials in parts of existing design, frequently necessitating considerable costly trial and error experimentation on an actual production basis. When, at the beginning of World War 11, it became apparent that mass production methods of forming would bc required in the aircraft industry if the large numbers of military aircraft needed were to be supplied, renewed attention was focussed on the problem of sheet metal formability. It was widely recognized that the formability requirements placed on sheet metals had been steadily increasing in severity through the years, especially as greater and greater emphasis was placed on streamlined designs with the resultant freer application of doubly curved surfaces. The recent advent of several new high strength aluminum alloys of more limited formability than some of the older alloys also served to emphasize the need for new approaches to the problem. It seemed evident that progress in the technology of sheet metal forming would depend to a great extent on the development of more reliable criteria for the evaluation of formability. Although the problem is admittedly very complex, the most logical approach appeared to be through studies of the fundamental material properties of sheet metals, especially under complex stress conditions simulating those prevailing in actual forming operations. Most previous investigations have failed to make full use of existing knowledge of fundamental material properties, and in many instances have attempted correlations with properties which are now recognized as being ambiguous in nature. This investigation was undertaken, therefore, with the aim of developing methods for the study of the flow and fracture of sheet meta1s under combined stresses, and of making use of such methods as might be developed in

Jan 1, 1947

By H. P. Willard, Conrad Martin

SINCE the deposits were found in 1927 in the Paradise Range of western Nevada, more than 1 mil- lion tons of magnesite and half a million tons of brucite have been mined and processed into a variety of granular refractory materials used as furnace linings by the steel industry. An additional million tons of magnesite were used during World War II to produce magnesium metal, and some magnesium oxide from the area is going into magnesia cements. Located near Gabbs, Nev., on the west flank of the Paradise Range, the principal bodies occupy an area a mile long by half a mile wide, and lesser occurrences have been found in a belt more than four miles long and in places almost two miles wide. Magnesite reserves containing less than 5 pct lime are estimated at more than 25 million tons. Reserves of better grade material are considerably less.

Jan 4, 1957

By Thos Stroup

RECENT contributions to the literature relating to the problems of coal mine management have discussed the pros, and cons of unionism among the miners as bearing upon the immediate problems of the industry, but have devoted singularly little thought to the underlying causes, and the fundamental reasons. for the remarkable growth of union sentiment among the miners, a growth paralleled only in the case of the railroad workers. It is all very well to revile their organization, its obvious stupidity and stubbornness, its multitude of economic and social crimes, but it is also well to realize that there have been deep-seated causes for all these things, causes that, while operating in all industries and amongst all workers, have in none of them found the optimum conditions for development such as exist in the coal mining industry. The rise of the United Mine Workers of America to a position of importance in the industry synchronizes roughly with the introduction of short-time operation; of course seasonal shutdowns and slow-time working have always been evident in our bituminous fields, but these evils have grown steadily worse since 1895 and the U. M. W. of A. has grown steadily stronger; yet short-time operation alone cannot account for this tremendous growth for, witness the signal failures that have always attended the attempts to organize the harvest workers, the fruit packers and other highly seasonal workers.

Jan 9, 1923

By T. M. Williams

DURING the year just ended we have had three great fires in the mines in the Wilkes-Barre district. One at the Empire Colliery, one at the Prospect shaft, and the other at the Baltimore old mine. It is proposed in this paper to give a brief history of the fire at the Empire Colliery, and the methods employed in extinguishing it. The fire was first discovered breaking out in the air-stack, alongside what is known as the " Kidder Plane," about one o'clock on the morning of December 31st, 1873. Subsequently it was ascertained that the fire originated in the return airway somewhere near the steam boiler, located inside the mine, near the head of No. 5 slope. The coal from this slope was hoisted to the shaft gangway, at a point nearly four thousand feet distant from the foot of the shaft. As there were from four to five hundred mine cars hoisted per day from this slope the steam boilers were located at this place. The mines being of considerable extent required a large volume of pure air for ventilation, and no fan having been erected at this slope at the time, the heat from the boiler was made use of to assist ventilation, by conveying the return air from No. 5 slope into the large airway made from these boilers to the surface through the old "Kidder slope" to the stack where the fire was first discovered. The length of this slope or airway was about one thousand feet, with a sectional area of about sixty feet. The quantity of air passing through it must have been over sixty thousand cubic feet per minute

Jan 1, 1875

By Warren Weaver

Some of the advantages of the inductive method of electrical prospecting were emphasized in a paper by Dr. Max Mason. Since this emphasis was misunderstood by some to indicate a too exclusive interest in inductive methods, we are especially happy to help correct this impression by reporting on some of our work on surface potential methods. Earth Currents and Surface Potentials When two electrodes, A and B, are placed on the surface of the ground a distance d apart, and a 100-volt battery is connected across the elec- trodes, current flows from the positive electrode A to the negative electrode B. The current does not pass directly from A to B along the straight line joining these two points. In fact, a negligible amount of the total current chooses this direct path, and the flow actually takes place

Jan 1, 1929

By T. E. Brower

SHORTLY after our previous paper on this subject was printed,1 we located a source of uncertainty in the results arising from the unexpected fact that hydrogen slowly reduces silica at 1100° C. in presence of iron, even when the iron nowhere touches the silica, although in absence of iron it does not do so. This difficulty has been completely obviated by the use of a small high-frequency furnace, which enables us to heat the specimen for analysis without raising the temperature of the silica vessel to a point at which any appreciable reduction of the silica glass occurs. We now describe this modification of procedure, and present some typical results obtained with it. For any given specimen of steel, the results are entirely definite and. reproducible, but their precise significance is still open to some question, as indeed is true of all methods of oxygen determination so far developed. Further elucidation of this question is to be expected from the cooperative comparison of the several methods now under way under the auspices of the Bureau of Standards at the instance of the Iron and Steel Division of the A.I.M.E.

Jan 1, 1934

By A. D. Brokaw

The so-called "paraffin dirt" of the Gulf Coast oil fields has been considered an indication of the possible presence of oil and gas, and not a few wells have been brought in solely on the basis of such evidence. In a sense, it may be empirically justified as evidence of the presence of oil or gas, though it cannot be said to be infallible. If the writer is correctly informed, its association with oil and gas was pointed out by Lee Hager some years ago, and while it is commonly mentioned by geologists and operators in conversation, no discussion seems to have found its way into print. The present interpretation is based on laboratory study rather than on field investigation, and is put forth with the hope of stimulating discussion which shall lead to more complete understanding. The term "paraffin dirt" has been applied to soils with a peculiar texture, which has been described as "curdy" or "rubbery." When moist, the material breaks much after the fashion of "green" cheese. It is rubbery under compression, but does not resemble rubber in tenacity or cohesion. When dry, the material ranges from hard clods to a horny mass of high tensile strength. The shrinkage in drying is very great, especially in the hornlike matter. The moist material ranges in color from dark brown in the specimens rich in organic matter to grayish in specimens containing more inorganic matter. All of the specimens studied were readily attacked by molds, which in some cases grew in great profusion on the samples. Samples exhibited a rather characteristic "swampy" or "mucky" odor when wet, and a characteristic odor of humic soils when moist. If the material is brought into suspension in water, very fine sand settles out and may be recovered by successive washing and decantation. The sand is almost entirely quartz, but contains occasional fragments of feldspar—more or less kaolinized and iron-stained. Practically all of the sand passes through a 100-mesh screen and the grains are extremely sharp —possibly below the limit of rounding. A flocculent mud, of clay and organic matter, remains in suspension for days. Some material is taken into solution in the water, imparting a slight tendency to froth when vigorously shaken. The results of partial analyses of four samples of "paraffin dirt," and, for comparison, one of a coastal plain soil are given in Table I.

Jan 1, 1920

By H. A. Coy

THE Mascot mines of the American Zinc Co. of Tennessee are situated in the Holston River valley, in Knox County, Tennessee, about 13 miles (20.9 km.) east of the city of Knoxville, and form a property of three operating shafts and one open pit. A second open pit is located at Jefferson City about 16 miles (25.8 km.) east of the Mascot mines. Geology Topography.-The principal topographical features of the region within which the zinc deposits occur is a series of parallel northeast and. southwest ridges which reach altitudes of 200 to 400 ft. (61 to 122 m.) above the valley. These ridges are formed of resistant formation such as sandstone, quartzites, etc., while the valleys are occupied principally by limestone, including Knox dolomite, and by shale and other formations subject to quick erosion. The Holston River valley is wide and open with a rolling surface. Sink holes are common to the limestone portion, the general aspect of the valley being that of well-rounded hills with low intervening valleys superimposed upon which is a characteristic sink-hole topography. General Geology.-According to Keith, the rock formation of the area extends from the lower Cambrian into the Silurian. The region has undergone severe deformation with heavy faulting, the underlying Cambrian having been brought to the surface by a series of low angle thrust faults, the strike of the faults and formations paralleling the general northeast and southwest direction of the topography and clipping at varying angles to the southeast. In general the Cambrian quartzites, sandstone, etc., occupy the ridges while the Cambro-Silurian dolomites, limestone and shales occur principally in the valleys. Of the latter, the Knox dolomite is of particular interest to this paper in that it is the ore carrier in the Mascot area. The ore is associated with more or less irregular breccia zones, the degree of brecciation varying from-a fine crushing to a breaking that involves blocks of large size. The breccia zones

Jan 9, 1917

By John A. Church

When, in 1879,I examined the mines of the Tombstone Mill and Mining Company, at Tombstone, Arizona, I found a bed of tailings containing 12,000 tons, which had a value of 9 to 12 ounces of silver per ton and some gold. The ore had been amalgamated in pans, in which each charge had been ground for four hours, having been pre viously stamped through rough-punched screens, which gave a pro duct varying from 1-100th to 1-20th of an inch, according to the state of wear of the screen. It was certain that a large proportion of the tailings must be in fine slimes, and the question of recovering their value was difficult. Even now the concentration of slimes is . an unwelcome task, and at that day very little was known about it. Nevertheless, after considering the results of a test by repanning the tailings, I advised the company to concentrate and smelt, although they had to face the difficulty of making a smelting-product from slimes containing only 3 per cent. of lead. Limestone was abundant enough, but no iron suitable for flux was to be had for hundreds of miles. One of the company's claims con tained an argeutiferous manganese-ore, which gave but poor results by amalgamation. This was one reason for recommending smelt ing ; for if manganese would play the part of a precipitant, as iron does, the company could smelt by combining two of its silver ores, without other flux than the small amount of lime that might be needed. At that time no smelter had ventured to trust manga nese as a precipitant, though large quantities of this ore containing silver were bought and used by custom-smelters, who looked upon the manganese solely as a basic flux for silica. I believe that no other furnace has been obliged to trust this metal, and that the man ganese practice of Tombstone remains unique among the records of smelting lead-ores in the shaft-furnace. The bright side of the problem was given by the fact that the mines were shallow and that the enterprise would at least begin with oxidized ores. The tailings contained about 85 per cent. of silica,

Jan 1, 1895

By R. Fawley, M. A. Quader, R. A. Dodd

Stacking fault energies and annealing twin frequencies have been measured for austenitic stainless steels having a) constant 20 wt pct Cr and varying nickel contents, and b) constant 20 wt pct Ni and varying chromium contents. The effect of nitrogen has also been studied and, to a lesser extent, so has the effect of carbon. All measured stacking fault energies plot linearly against the corresponding annealing twin frequencies, suggesting that, for constant prior deformation and grain size, twinning frequency can be used to estimate stacking fault energy. Compositions low in nickel possess the lowest fault energy, while the maximum fault energy within the investigated composition range occurs mound 20 pct Cr-20 pct Ni. Nitrogen has practically no effect on stacking fault energy when increased from 0.005 to 0.05 wt pct, although Planar dislocation glide is associated with higher nitrogen contents; this may be a short-range order effect. Carbon may raise the stacking fault energy a little, and causes pronounced dislocation tangling in deformed alloys. The basically different dislocation structures promoted by nitrogen and carbon, respectively, are not associated with large variations in stacking fault energy, and the reason for the difference remains unknown. INTEREST in the dislocation configurations developed in plastically deformed alloys arises principally from a desire for an understanding of mechanisms of plastic deformation and fracture. Comparatively little basic work has been concerned with austenitic stainless steels, although considerable interest has developed in the fundamental aspects of deformation of these alloys since the suggestion that those compositions deforming essentially by planar glide are particularly prone to transgranular stress corrosion cracking.' Certain facts are well-established. An 18 Cr-8 Ni steel (type 304) has a low stacking fault energy which is increased by higher nickel contents, and the structure of these steels when moderately plastically deformed changes concomitantly from planar to less planar to distinctly tangled dislocation configurations. These changes are thought to relate to changes in stacking fault energy, and considerable effort has been expended in measuring stacking fault energies of austenitic stainless steels through the determination of node curvatures2"4 even though the method has limitations due to formula approximations,5 an upper limit of measurement of 50 erg cm-2 at the most,5 and the necessity of an extremely meticulous experimental technique. Therefore, it is not surprising that only qualitative agreement between different investigators is generally to be found.'-' At high energies where node radius measurements are inappropriate, some use has been made of annealing twin frequencies to estimate relative stacking fault energies, although a recent critical evaluation of the method suggests that it should be used cautionsly with due regard to effects of grain size and prior deformation.6 Finally, there is a question as to whether the structures of some deformed steels are due to ordering effects. In particular, the role of nitrogen in promoting planar dislocation motion has been suggested to be due to ordering,' but similar suggestions have been made for steels having low interstitial contents.4 EXPERIMENTAL Small ingots of austenitic stainless steels (-50 g) were prepared from components exceeding 99.99 pct purity, the nickel and chromium being Johnson Matthey "Specpure" metals. Carbon was added as pure graphite, and nitrogen as CrN. The components were accurately weighed, and it was assumed that the final composition was the same as the nominal composition

Jan 1, 1969

By James E. Little

Of the several extensive deposits of brown iron-ore in Cuba, including those of Mayari and Moa, that of Mayari was the first to be systematically explored, and was selected as the scene of the first operations in the development of this class of ore. Construction-work, begun in the spring of 1907, involved the building of 16 miles of stantlard-gauge railroad and two large double-track inelines, the installation of milling-machinery, a nodulizing-plant, power-plant, shops and shipping-facilities, and the dredging of an extensive basin for deep-draught vessels. Unusual weather-conditions delayed the completion of portions of this work so that the entire plant was not in operation until December, 1900.

Jan 1, 1912

By Schlumberger, C

IN the search for practical geological problems amenable to solution by the potential methods, the geophysicist is led to study mathematically various theoretical cases. In these idealistic discussions, the media under consideration are generally supposed to be homogeneous and iso-tropic. The geophysicist, of course, realizes perfectly that these condi-tions do not occur in their entirety in reality. However, the assumptions made are justified, because very often they are necessary in order to render possible an exhaustive study of a given problem, which otherwise would be too complicated, and would not lend itself to a complete mathe-matical analysis. Of the above two assumptions, that concerning the homogeneity of a given geological formation is satisfactorily realized except in so far as isotropy is concerned, since this property is not often encountered in practice. As a consequence, it is very desirable for the geophysicist to have quite an extensive knowledge of the properties of anisotropic forma-tions, and of the laws that govern the propagation of electric current therein. With such principles in mind, he will be able to decide whether the conclusions arrived at in simple, isotropic conditions are still correct in more complex cases, or in what way they must be modified or adapted in order to constitute a sound basis for the interpretation of the results obtained in anisotropic media. On the other hand, the fact that in anisotropic formations themobility of the ions is greater along the strike than perpendicular thereto can be utilized for determining the direction of the dip by induc-tion measurements. We therefore propose to study in three successive chapters the following points: 1. Propagation of the electric current in anisotropic media. 2. Some consequences of the anisotropy of geological formations with reference to the surface electrical measurements, and their interpretation. 3. Determination of the direction of the dip of anisotropic formations by surface induction measurements.

Jan 1, 1933

By Charles Pack

Extensive progress has been made in the metallurgy of alloys for die castings. Enthusiastic proponents of some alloys are inclined to make extravagant claims for their materials, which may be justified by physical tests on test bars made from the respective alloys but are seldom justified by the results obtained with commercial die castings made from those alloys. Chemical analysis of the test bars and castings fails to determine the cause of these variations, since they are due to other physical factors entering into the commercial production of die castings. In this paper, an attempt will be made to outline some of the factors in commercial die-casting practice to which these variable results may be attributed, in the hope that the manufacturer of die castings, recognizing the importance of these factors, will devote more attention to them in the design and construction of dies and equipment. In 1914,l the author defined die castings as "metal castings made by forcing molten metal, under pressure, into metallic molds or dies." This definition was given in order to differentiate die castings from other molded metal products such as "permanent-mold" castings, L'slush" castings and similar products that are sometimes erroneously termed die castings. The term "die casting" could be interpreted to include all castings made in metal molds or dies; but since this term, like most of our technical nomenclature, has been developed by commercial practice we must look to this practice for its proper definition. The Germans, with their usual devotion to desecriptive names, have adopted the name of sprilzguss (squirt cast) for die castings. Undoubtedly this name is more descriptive of the die-casting process, where the metal is literally squirted into the die and serves to differentiate this process from other metal mold processes, where the metal is poured into the die. In the earlier paper mentioned, the author also emphasized the fact that the definition given for die castings indicated clearly that the satisfactory operation of the process must comprise three factors, all of which must be considered of vital importance to the successful operation of the die-casting process:

Jan 1, 1931

By A. S. Adams

A glance at the list of papers1 that have been published since 1920 on the general subject of flotation suggests the variety of ideas that exist regarding the underlying cause of the phenomenon. Among these ideas, we find several coherent theories, but none that adequately and completely explain the phenomenon. Ralston2 and Bains3 suggested an electrical theory which has to do with the attachment of mineral particles to a bubble by the attraction of unlike electrical charges. This theory has its root in the fact that a bubble of air in pure water is electrified in such a way that the surfacc is negatively charged while the body of the water is positively charged. This result, which was first discussed by Helmholtz, also obtains when the water contains anything except a high concentration of hydrogen ions, or ions which are trivalent or tetravalent. The theory also holds that the mineral particles have positive charges on their surfaces, and so there is attachment between bubble surface and mineral particles by the old law of electrostatics, which states that unlike charges attract. Contact Angle and Oil Attraction The contact angle—the angle formed by a fluid-fluid boundary when both are in contact with a solid-—has been indicted several times for complicity in the phenomenon of flotation. This angle is supposed to indirectly measure the surface energy of a solid. Thus if we have two fluids in contact with a solid, we may express the difference between the two fluid-solid tensions as equal to the fluid-fluid tension times the cosine of the angle between the two fluids.4 If the two fluids are in contact with the solid, this is, no doubt, an excellent way of establishing relative surface energies. However, in flotation, we deal with substances which are not wetted by water. What assurance have we, then, that the angle

Jan 1, 1928

By H. G. Doll

A new electrical logging method is described which measures the resistivity of small volumes of material near and behind the wall of the bore holes. The very small electrode systems used are supported in the face of the flexible insulator pad of appropriate dimension maintained in contact with the wall. The measurements are recorded simultaneously with two different electrode spacings. This method provides a very detailed record of the formations and particularly of the permeable beds traversed by the bore holes. The application of MicroLog to the location of permeable zones within compact formaltions, such as limestone, and to the determination of the amount of sand existing in sequences of thin shale and sand streaks is discussed. The possibility of quantitative determination, providing a step toward the evaluation of formation porosity and mud cake thickness, is also examined. Field examples illustrate the essential features of the method. INTRODUCTION In conventional electrical logging, the spontaneous potential (SP) log is used to delineate the permeable beds, and the resistivity logs are used primarily to provide indications concerning the fluid content of the beds. When the formations are much more resistive than the mud, as happens, for example, in limestone fields, the SP currents are short-circuited by the more conductive mud column, with the result that the SP log is quite rounded. In that case, the SP log generally gives the approximate location of the permeable formations but it cannot be used for an accurate determination of the boundaries of each permeable bed.' Solutions for the problem of obtaining a better determination of the permeable beds in limestone fields were developed from two angles. One approach consisted in improvements to the logging of the SP, as given by Selective SP logging and Static SP logging. These new methods, which have been described in an earlier paper,' give good results when the mud is not too salty, but they are still in a somewhat experimental stage, mostly because the development efforts have lately been concentrated on another approach to the problem, i.e., the MicroLog.

Jan 1, 1950

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525'C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine' and LOW.' Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468'C, hold 72

Jan 1, 1969

Jan 1, 1887

By C. E. Lundin, M. Hansen, D. J. McPherson

PRIOR work on the Zr-Cu phase diagram by Alli-bone and Sykes,' Pogodin, Shumova, and KUGU cheva,' and Raub and EngeL3 as confined largely to copper-rich alloys. The investigations of Raub and Engel were the most recent and seemingly the most complete of these. Alloys from 0 to 68.3 pct Zr were studied principally by thermal analysis and microscopic examination. These authors reported an inter metallic compound ZrCu, (1116°C melting point) and two eutectics, one at 86.3 pct Cu (977°C mp) and the other at 49 pct Cu (877°C mp). The solubility of zirconium in copper was reported to be less than 0.1 pct at 940°C. The zirconium melting stock consisted of Westing-house "Grade 3" iodide crystal bar (nominally 99.8 pct pure). It was treated by sand blasting and pickling (HF-HNO, solution) to remove the surface film of corrosion product, resulting from grade designation tests. The crystal bar was cold rolled to strip, lightly pickled again, and cut into pieces approximately 1/32 in. thick and 1/4 in. square. These were cleaned in acetone, dried, and stored for charging. The high-purity copper (spectrographic grade) was supplied by the American Smelting and Refining Co. with a nominal purity of 99.99 pct. These copper rods were rolled to strip, cut into squares the same size as the zirconium platelets, cleaned in acetone, dried, and stored. Equipment and Procedures The equipment used for melting and annealing the zirconium binary alloys and for the determination of solidus curves has been described in connection with previous work on the Ti-Si system' and in recent papers in this series describing the studies on eight binary zirconium systems.5-' Techniques employed for preparing and processing the alloys were also similar to those used in the above references. Ingots of 20 g were melted under a protective atmosphere of helium on water-cooled copper blocks in a nonconsumable electrode (tungsten) arc furnace. The ingots were homogenized and cold-worked prior to isothermal annealing to aid in the attainment of equilibrium. The specimens were heat-treated in Vycor bulbs sealed in vacuo or under argon, depending on the temperature of the anneal. Quenching was accomplished by breaking the Vycor bulbs under cold water. Temperature control was within ±3OC of reported temperatures. Thermal analysis was primarily relied on to determine eutectic levels, peritectic levels, and compound melting points. The induction furnace incipient melting technique was also used but did not provide the accuracy obtained by thermal analysis in this system, which involves much lower solidus temperatures than the other zirconium systems. A special technique for the determination of characteristic temperatures was employed in the case of several intermediate phases and their eutectics which displayed very small differences in melting temperatures. Specimens were sealed in Vycor bulbs and annealed at a series of very accurately controlled temperatures. Metallographic examination was then employed to reveal incipient melting. Furnaces and techniques in general were described previously.' The echant used was 20 pct HF plus 20 pct HNO3 in glycerine unless otherwise stated. Results and Discussion The chemical analyses of the majority of alloys prepared for the determination of phase relationships in this system are given in Table I and a brief summary of the equilibrium anneals employed is given in Table 11. In a preliminary program, alloys containing 1, 4, and 7 pct Cu were annealed for three different times at each of the temperatures 700°, 800°, and 900°C. No change in the relative amounts of phases present was detected after 350, 150, and 75 hr at the above temperatures, respectively. The times listed in Table II were accordingly chosen as a result of these preliminary tests. Zirconium-rich alloys containing from 0.1 to 10 pct CU were reduced by cold pressing from 58 to 8 pct, depending upon thk alloy content, homogenized for 7 hr at 900°C, and then reduced 80 to 13 pct by cold rolling, again depending upon copper content. Other alloys were studied in the cast, or cast and annealed conditions. The contracted scope of investigation for this system included the range 0 to 50 atomic pct Cu. This approximate region is shown in Fig. 1. Due to evidence of phase relationships departing considerably from those proposed by Raub and Engel" in the 50 to 100 atomic pct range, the investigation was extended to cover this composition area rather thoroughly also. Fig. 2 is a drawing of the entire diagram. The labeling of some phase fields was omitted in Fig. 2 for the sake of clarity. An expanded view of the zirconium-rich region, with the experimental points necessary for its construction, is given in Fig. 3. The generally accepted value of Vogel and Tonn8 or the allotropic transformation a + 862' ±5OC, was employed in the construction of these diagrams. A careful study revealed that the "Grade 3" crystal bar used in this investigation actually transforms over the approximate range 850" to 870°C, due to impurities. It must be expected that this two-phase field in unalloyed zirconium will cause some departures from binary ideality in the very dilute alloys. Zirconium-rich Alloys: The a + ß transformation temperature is decreased from 862" to about 822°C by increasing amounts of copper. Thus, a eutectoid reaction, fi ß a+ Zr,Cu, occurs at a composition of about 1.6 pct Cu. The eutectoid level was determined to lie between the alloy series annealed at 815" and 830°C. The placement of this eutectoid temperature

Jan 1, 1954