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By Sidney H. Loram

As the work carried on by this Company, of which the writer has been in charge for the past two years, is somewhat unique, the following account of it may be of interest, and, on that account, is offered to the Institute without any attempt to claim this practice as the best. Mines. The mines supplying ore to the Company arc situated in three groups: the Guanaco field,.about 80 miles N.E. of the port of Taltal (lat. 25" S., long. 70" 30' W. of Greenwich); the Sierra Overa, about 63 miles S.W. of Taltal; and Paranao, about 42 miles due N. of Taltal (12 miles N. of the small town of Paposo, once famous for its copper-output). Guanaco. This field lies in the center of an absolutely waterless mountainous desert, where not a sign of vegetation can be found for miles. The dryness is such that ivory and horn crack and open, while raw-hide must be used in place of leather, which -would become worthless in a very short time. Water is brought about 21 miles by piping from the Cordillera, but only in small quantities, and costs in the Guanaco $7 (= $1.78 gold) per cubic meter. All supplies and food are sent from the port of Taltal, which in turn draws its supplies from the south of Chile, the

Jan 1, 1900

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,' but neglected one2' which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970

By K. Y. Lo, R. S. C. Wai, R. K. Rowe, L. Tham

Laboratory tests for the determination of thermo-mechanical proper- ties of three rock types were performed at temperatures up to 400°C. Results showed that for the medium and coarse Granitic Gneisses, the coefficient of thermal expansion and Young's modulus are strongly temperature and temperature history dependent. A threshold temperature exists for each rock type above which material nonlinearity becomes important, and is associated with the progress of thermal cracking. Finite element computations were performed to illustrate the influence of material nonlinearity and boundary constraint on thermal stresses. Finally, a case history of thermal spalling was analyzed and it is shown that the results of analysis are consistent with field observations.

Jan 1, 1982

By R. J. Colony

THE failure, or disintegration, of concrete in structures, even when the cement, sand, and coarse aggregate used have passed satisfactorily all tests and inspections, is not uncommon. Such failures occur even when proper methods of mixing and placing have been used and where, weather conditions were correct. In these cases, the origin of the trouble must be sought in the cement, therefore some additional mode of determining the quality of cement must be employed. The problem is to find a simple, usable; easily applied method that will supplement the standard tests. The solution of this problem in-volves a knowledge of the chemical composition of Portland cements, also of their constitution (or componental composition), as the behavior of a cement, when gaged, is dependent on the physical and chemical characters of the compounds of which it is composed, the proportions existing between them, and the fineness of grinding. It is likewise essential to know the character, behavior, and composition of the hydration, products of Portland cement. The most promising method of attack makes use of chemical, mechanical, and petrographic methods. Chemical, by determining quantitatively not only the usual constituents, but the carbon dioxide and water. Mechanical, by determining the fineness with the air analyzer,1 which separates into fractions of various grain dimensions all of that portion, which in the ordinary sieve test passes the 200-mesh sieve and constitutes at least 75 per cent. of the total cement. These fractions may be further studied chemically and petrographically and micrometric measurements made of the grains. Petrographic, by the method of immersion, and by making thin sections from test pats of both neat cements and standard` mortars.

Jan 1, 1921

By Charles H. Osmond

The rapid progress of basic changes in refining processes, which has characterized this division of the petroleum industry during the last 7 years, slowed up in 1926 and the industry as a whole devoted itself to the enormous task of adopting these changes to its methods of manufacturing. If for no other reason, the year of 1926 will stand out as the first year of widespread activities in placing refining on a true manufacturing basis. A brief survey of each of the important operations and the trend of the changes with their economic results indicate the importance of this period of transition. No attempt has been made to detail the numerous activities in each of the major operations and the writer would refer those seeking such information to the various trade papers and the paper on "Basic Changes in Refining Processes," by Walter Miller.' Distillation.—-Distillation (excluding cracking) is the major item in refining. During the past year there has been a wide application of the improvements developed in former years. Operating costs have been reduced for fuel, labor and capital items. Practically all types of distillations are now carried on as semi-continuous or continuous operations, rather than by the old batch method. Heat-saving devices, such as heat exchangers, or improved combustion chambers, have had a marked effect on the total fuel bill of the industry. The modern pipe-still has been widely used and figures available show that approximately 10 per cent. of the older shell equipment was replaced by pipe-stills during 1926. The range of usefulness of this type of equipment has been extended successfully to the most complicated types of lubricating oil manufacture. These stills afford marked economies in fuel as well as labor costs, also many advantages in older plants where space is limited, as a single pipe-still can replace several batteries of shell stills. Capital expenditure per barrel capacity is decidedly lower and offers economy in this direction. Although there has been considerable discussion of other types of distillation equipment such as the vacuum still, there has been no appreciable increase in these installations during 1926. Cracking.—-Cracking equipment increased rapidly during 1926 as evidenced by the increase in output of cracked gasoline from an average

Jan 1, 1927

By F. C. Newton

RefineRs of lead by the Parkes process have always been solicitous of recovering the zinc used in the desilverization, and justly so, as the loss in zinc constitutes one of the heavy costs in this method of refining. Part of this loss is due to the absorption of zinc by lead, and in the present state of knowledge is not recoverable as metallic zinc. The remainder of the zinc, which finds its way into the precious-metal-bearing crust, is recoverable and naturally engages the operators' most exacting attention. Careful elimination of the impurities in base bullion has enabled the refiner to produce a zinc crust better adapted to retorting, which reflects favorably in the zinc recovery;- and to produce a richer crust, thereby lowering the zineking cost, as the increased efficiency of the zinc results in less of it being in circulation. It is obvious that if the ratio of concentration be increased, a lessening of the amount of crust formed will ensue, throwing less work on the retorts and diminishing the amount of retort metal sent to the cupels, thus making an actual money saving in all these operations. In the effort to obtain a rich crust, the metallurgist has increased the heat to a considerable degree, upon the assumption that at the higher temperature the zinc-dver alloy could be squeezed free from the adhering lead. A further possibility for improvement suggested itself in the freezing-point curve of Prof. H. C. Carpenter, upon zinc and silver. Study of this curve disclosed the existence of a definite chemical compound, Zn3Ag2, with a freezing point of 665" C., a promising compound for practical application. In the experiment undertaken it was endeavored to force this compound into the crust, hoping thereby to obtain a higher concentration than formerly. It was recognized that in bringing a large kettle of lead to such a heat, more fuel would be used, the life of the kettle would perhaps be shorter, and other disadvantages would be experienced. AS a commercial operation, the project would have to stand on its own feet,

Jan 1, 1915

R. H. SWEETSER, Columbus, Ohio.-My experience with oxygen in the blast is limited to the use of one tank of oxygen in melting out a chilled anthracite furnace. The oxygen was introduced through the peephole of the tuyeres and opened them in a very short time. We could see that an intense heat was generated just as soon as the oxygen struck the fuel. I agree with the committee in respect to many. of the things that will probably happen in the iron blast furnace, particularly as to the speeding up of the operation. There will undoubtedly be changes in the shape of the blast furnace, and if I were designing one today I should hesitate about the form to give it. Mr. Kirby suggested that the proper shape might be rectangular. Some of the men of the American Rolling Mill Co. have reached the same conclusion, as a result of Royster and Joseph finding that the combustion zone in the front of the tuyeres extended into the furnace less than 40 in. If this is correct, we might build the furnace with an elongated rectangu-ular hearth having the shorter dimension a little over 80 in. and secure. a very intense temperature in the hearth. The committee's report said, "With more oxygen available in the blast, the smelting ability of the furnace will be increased beyond the' speed of the preparing zone in the shaft." This can be controlled by providing ample facilities for getting stock into the furnace, and this will be one of the biggest changes in blast-furnace construction. The question has been raised as to finding suitable refractories to withstand the increase of hearth temperature. If the furnace can be kept full, the descending column of cold material will probably take care of the increased heat from more rapid combustion of the coke. At the Cleveland meeting, in 1912, the iron blast-furnace men listened with great interest to a paper on copper slags; from Mr. Kirby's paper, it looks as though they might again have to go to the copper men, for many of the problems of the iron blast furnace of the. future that uses oxygen may be worked out on lines of the copper blast furnace.

Jan 11, 1924

By R. A. Corley, W. R. Wilcox, J. R. Teviotdale

Chemical vapor deposition of hafnium carbide yielded whiskers, needles, dendrites, faceted crystals, and adherent coatings. The gas stream compositiom and the mass transfer conditions determined the habit of the deposit. The deposits were obtained at temperatures ranging from 1100" to 1800°C. HAFNIUM carbide has the highest melting point of any binary compound; therefore, its various potential applications are a subject of vital interest to the aerospace industry. The experiments described herein were performed to investigate the chemical vapor deposition of hafnium carbide with particular interest being placed upon the possible production of high-strength single-crystal whiskers for composite materials. In 1931 Moers 1 used a gaseous mixture of HfC14, Hz, and toluene to vapor deposit crystalline hafnium carbide on a tungsten filament heated to 2400°to 2800°C. More recently Lepie 2 deposited hafnium carbide on graphite using HfC14 and methane in a helium gas carrier. The pyrolytic depositions described here were accomplished in graphite tubes by using various gas mixtures and dopants. The resulting crystal habits included whiskers, needles, needle dendrites, bulbous dendrites, faceted crystals, and smooth, adherent poly-crystalline layers. EXPERIMENTAL The depositions were carried out in an induction-heated graphite tube, 1.2 cm ID, which was contained in a vertical 9-cm-ID quartz tube. (A more detailed account of the experimental procedures and results is given in Ref. 3.) Refractory oxide fiber and tubes and graphite felt were utilized jointly and singly for therma1 insulation. A typical temperature distribution is shown in Fig. 1. The reactant gases were introduced at the top and removed at the bottom of the tube. Table I summarizes the experimental conditions and results. Many deposition habits were obtained. X-ray analyses showed that they possessed the hafnium carbide structure. Almost invariably these formed well above the point of maximum temperature in the graphite tube. The habit depended strongly on the gas composition. In a series of runs (e.g., run A) using HfC14 and toluene in H 2, hafnium carbide coatings, Fig. 2, were reproducibly obtained at the position where the tube wall was 1400°C, and bulbous dendrites, Fig. 3, were

Jan 1, 1969

By Frederic L. Kadey

Perlite, as a volcanic glass, has been recognized since the Third Century, B.C. (Langford, 1978). The precise details of discovery often become lost in antiquity, and the variations among the stories pertaining to the more recent discovery of perlite as a material of commerce are no exception. Credit in the United States is given to a dentist who, while experimenting with tooth enamels about 1941, discovered that perlite-the rock-intumesced when subjected to heat. At about the same time it is reported that the chief geologist of Silver and Barytes Ores Mining Co. attempted to put out a picnic bonfire on the shores of Milos Island, Greece by throwing beach sand on it. The ensuing pyrotechnic display immediately conjured up in that man's mind the possibility of a new use for the volcanic rock that constituted most of the island. Very little was done with this discovery either here or abroad until after World War II. Today the name perlite is applied to both the hydrated volcanic glass, generally of rhyolitic composition, and to the lightweight aggregate that is produced from the expansion of the glass after it has been crushed and sized. Petrologically, it is defined as a glassy rhyolite that has a pearly luster and concentric, onionskin parting. Occurrences of perlite are restricted to several Tertiary to Quaternary age rhyolitic belts that trend in a generally north-south direction around the world. Commercially suitable deposits generally occur as domes of several hundred feet in height, although glassy zones in welded ash-flow tuffs and others associated with dikes and sills also have been reported. Mining is by ripping and blasting from open pits. Because of weight considerations, perlite usually is shipped to the local market area for subsequent expanding. In the United States, New Mexico leads in production with Arizona, California, Nevada, Idaho, and Colorado following in approximately that order. The principal use for expanded perlite is as a lightweight insulating aggregate in cryogenics, in plaster, concrete, and in loose fill insulation. Expanded perlite is also used in horticultural applications, and after subsequent milling and classification, as a filter aid. The United States is the world's largest producer and consumer of perlite. Table 1 shows the world production of perlite and Table 2 shows the perlite mined, processed, expanded, and sold or used by producers in the United States. Geology Composition and Morphology Any discussion of perlite must take into consideration its dual nomenclature, for it is known by the same name as both the naturally occurring rock and, after processing and expansion, as the lightweight aggregate of commercial significance. In its naturally occurring form, perlite is a rhyolitic glass that contains from 2 to 5% combined water. While perlite also can occur as andesitic or dacitic glass, these latter types are of negligible commercial significance. Table 3 lists the chemical composition of a few typical perlites (Anderson, et al., 1956; Langford, 1979). What sets perlite of commercial significance apart from other volcanic glasses is the fact that under the proper conditions of preparation-crushing and sizing-it will, when rapidly introduced into a flame of sufficient temperature, expand or "pop." All of the elements of composition contribute to the expansibility of the rock. The role of the combined water, however, is the most significant because it is believed not only to produce a fluxing effect in the softening of the highly siliceous glass prior to expansion, but it is also responsible for the explosive force of expansion through volatilization during heating. The current theory of the origin of the water in perlite is now less con-

Jan 1, 1983

By F. H. Willcox

In Bessemer-steel practice, air is blown through a bath of iron, or projected strongly upon its surface to burn out silicon, manganese, and cafbon. Toward the end of the blow, when the iron is not protected from oxidation by these elements and the excess of air becomes great, there is oxidation of the iron. In open-hearth practice, the same difficulty is experienced with dissolved gas and oxides in the product, though not to as great or severe a degree as in the Bessemer process because the oxidizing conditions grow less severe as the end of the heat is approached, and if the bath is allowed to boil for a time it undoubtedly frees itself from a large part of the gas and oxides which have been absorbed in the earlier part of the process. Basic open-hearth steel is usually assumed to contain a larger proportion of oxides than acid open-hearth steel, but it may be said that all steel, Besserner and open-hearth, contains more or less oxide of iron dissolved in the fluid metal at the end of the "blow" or "heat." That certain metals are solvents for their respective oxides has been shown, in the case of copper, by Heyn, and, in the case of iron, by Law. It is indicated that the solubility of iron oxide in iron increases with the purity and temperature of the metal. This confirms what is observed and known by operating men, and these observations may be summarized as follows: 1. Cast iron. is rarely subject to oxidation, as is logical from its composition. 2. Normal steel, unless deoxidizers are added, contains blow holes. 3. Steel known to be oxidized is full of blow holes. 4. The addition of deoxidizers prevents, to a greater or less degree, the formation of blow holes in normal steel. With these observations in mind, it is logical to deduce that the cause of blow holes lies in part in the presence of dissolved oxide of iron in the molten steel and its consequent reaction with the carbon of recarburizers, when these are added, to form gases. (Another factor in the origin of blow holes is, of course, the solubility of gases themselves in the steel and

Jan 1, 1917

THE primary interest in the subject of this chapter lies in the fact that various heats of steel made to the same chemical specification do not always have the same properties. We are referring here, of course, to properties inherent in the just solidified ingot and are not considering variations in properties caused by variations in subsequent mechanical or thermal treatment. The expression "made to the same chemical specification" is used because some of the variations in properties are due to variations in chemical analysis within the specified ranges of those elements commonly specified and determined. In plain carbon steels these elements are ordinarily not more than five: carbon, manganese, silicon, phosphorus, and sulphur. In alloy steels the special alloying elements also are specified and. determined. It might be thought that variations in properties due to such variations in ordinary chemical composition are to be expected, well understood, and hence not in need of discussion in this chapter. It will be considered here, however, that this phase of the subject is not always wholly clear. Furthermore, it certainly seems profitable to seek the explanation of anomalous properties in the ordinary chemical composition of the steel before looking into less well understood variables of open-hearth practice. It is sometimes surprising to learn that some puzzling variation in properties is caused merely by a variation in the ordinary analysis of the steel. This surprise is apt to be due not to general lack of knowledge of the effects of the composition of steel upon its properties but rather to the fact that we do not happen to have been previously much concerned with the particular property under consideration. For example, if we are accustomed to using S.A.E. 1035 bars for applications which depend chiefly on the stiffness, strength, and toughness of the steel in the as-rolled condition, we might quite logically develop the conclusion that variations in carbon content from 0.30 to 0.40 per cent are not significant. Then if we later have occasion to make heat-treated bolts of the same grade of steel, we may be surprised to

Jan 1, 1944

By Sir Robert Hadfield

LAST year this Institute was good enough to accept some remarks by the writer regarding sound steel, entitled Plant for Hadfield Method of Producing Sound Steel Ingots, being a continuation of a research in which for some time the writer has been engaged, and full particulars of which were submitted in papers entitled A New Method of Revealing Segregation in Steel Ingots, and Method of Producing Sound Ingots, read before the Iron and Steel Institute in October, 1912. These papers gave rise to a very interesting discussion, both in England and America. This question is one of vital importance, as unless sound steel in the form of ingots is first obtained, sound steel in the finished forms of rail billets, rails, bars, sheets, and other forms cannot be expected. The working stresses demanded by modern conditions are so great, each year they probably approach nearer to the limit of safety, that without doubt those who produce steel will be compelled to pay the attention which this subject deserves. Moreover, the problem is not an insuperable one, as shown by the writer in the papers above referred to. In view of the information which has already been presented in these papers, it is not now necessary to go into details of the system advocated by the writer, except to repeat that the ingots and steel now referred to were produced by employing in the first place sound fluid steel, free from blowholes, this being poured into ordinary ingot molds, provided with the necessary feeding heads, the insulating slag medium, also charcoal and air blast or other suitable form of applying heat to the head portion of the ingot. Tile upper or head portion of the ingot is kept fluid by the intense heat generated by the air blast and charcoal, so that such fluid steel passes into the body of the ingot below the head, thus feeding and avoiding the shrinkage or piping which would otherwise occur. The result is the production of a sound steel ingot, free from blowholes, segregation and piping, and in which the waste portion, usually termed the discard, is but little over 7 or 8 per cent.

Jan 4, 1914

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.'' The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-' "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By AIME AIME

MINING geology was granted two sessions, Wednesday morning and afternoon, Feb. 17. The morning session, at which H. Foster Bain presided. first considered Paul M. Tyler's paper, "Economic Notes on Steel-making Alloys." The elements used in these important alloys are chromium, manganese, molybdenum, nickel, phosphorus, silicon, titanium, tungsten and vanadium. Edward Sarnpson and C. K. Leith asked whether chromite concentrates could be used, Mr. Tyler replying that they could if not too high in iron. G. W. Pawel said that they were used at Niagara Falls, nlixecl with coarse ore. In reply to a question asked by A. O. Hayes, Mr. Tyler said that molybdenum had not affected the price of tungsten. After this discussion, E. S. Moore's paper on nickel was considered. H. Foster Bain thought that nickel is well controlled and in good hands, technically and politically. The popular stainless steel in America is the 18:8 Cr-Ni metal. In Germany a Cr-Mn steel has possibilities. It is easy to make, cheaper. has better workability, will stand 85 per cent reduction between heats.

Jan 1, 1932

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,' in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.' have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.' Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.''-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

By C. S. Yust, C. S. Morgan

ThIS note reports the observation of masses of dislocation etch pits around the weld necks of small single-crystal particles of calcium fluoride sintered to a cleaved face of a larger CaFz crystal. Crystal particles in the -50 +I00 mesh size range were placed on freshly cleaved CaFz surfaces and heated at 1250°C for 30 min in a tantalum container in an argon atmosphere. The sintered specimens were then etched at room temperature for 40 to 50 min in a 2 pct sulfamic acid solution which is a selective etch for dislocations in caF2.' Figs. 1 through 3 show the masses of dislocation etch pits observed around weld necks after etching. In some cases, particles were gone after removal of the specimens from the furnace although weld necks were readily visible. In other instances, no etch pits formed around a weld neck. A possible cause of concentrations of dislocations on the crystal surface is mechanical deformation of the base crystal when particles are dropped on it. If such a deformation does occur, it would be much smaller than that caused by the light punching of a crystal with a sharp instrument which results in large concentrations of etch pits. However, crystals deformed by punching with the sharp instrument and annealed at the conditions of these experiments (1250°C for 30 min) before etching showed no concentrations of dislocation etch pits. It is obvious that dislocations from the much smaller deformations, possibly created when particles are placed on the surface, would also anneal out. Etching of large crystals which had particles placed on them in the usual manner but which were not heated showed no dislocation concentrations such as shown in Fig. 1. The magnitude of dislocation etch-pit concentrations did not vary with extensive variation of the cooling rate. The appearance of many of the etch-pit clusters is typical of a well-annealed condition, indicating that the dislocation concentrations formed before the specimen temperature was lowered. Therefore, it is evident that thermal stresses in the neck area did not create the deformation indicated by the presence of the dislocations. The possibility exists that the etch-pit concentrations at places where particles had been removed may be the result of deformation accompanying the fracture of the sintered bond. That this is not so was demonstrated by breaking off particles around which no etch pits occurred. Re-etching never resulted in the large concentrations observed at sintering sites. The stress available to effect material movement during sintering of two particles will depend on the geometry at the contact point but can easily exceed the macroscopic yield stress in CaFz systems. It appears that the plastic deformation observed results from sintering or simply from the weight of the small particles. It has been previously argued that plastic flow makes an important contribution to the initial densification of oxides having the fluorite crystal structure.2p3 If plastic deformation occurs, it would begin as soon as the temperature is sufficiently high

Jan 1, 1967

By Walter F. Bradley

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

Jan 1, 1935

By Martin Epner, Eric Gregory

DURING the past decade, considerable work has been carried out on various cermet systems in an effort to produce materials suitable for high-temperature applications in gas turbines. Most of the materials have not, as yet, met the requirements of the engine manufacturers, primarily because of their lack of room-temperature ductility and thermal shock resistance. In the field of tool materials, however, although ductility is still of prime importance, much has been accomplished by improving design parameters and the quality of carbide materials with a view to using cermet compositions successfully. The systems described in this paper were designed primarily for application in this field, although their development was a natural outcome of work on similar compositions designed for high-temperature service. In steel-bonded titanium carbide, the steel binder imparts heat treatability to the system while the carbide provides abrasion and wear resistance. Combining the carbide and the steel matrix in carefully controlled proportions results in a composite material which, when the steel is hardened, has man of the properties of cemented tungsten carbide. In the annealed condition, this material can be readily machined by the conventional chip-removal techniques. Titanium carbide has certain distinct advantages over many of the other carbides when combined with a steel matrix. It is among the hardest of the carbides and is one of the most stable. Liquid iron wets titanium carbide, and this wetting assists in the formation of a dense cermet. Once the composite structure has been formed, the titanium carbide acts as a relatively inert phase during the heat treatment of the matrix. PREPARATION OF ALLOYS The steel-bonded titanium-carbide materials described in this paper were prepared by the liquid-phase sintering technique. The titanium carbide used had an average particle size of 6 to 7 p, a total carbon content of 19.4 pct and 0.35 pct free carbon. This was blended with the elemental metal powders by ball milling them together in a hexane medium. After drying, paraffin wax was added to the blend to provide green strength in the pressed briquettes, and compacting was performed at 15 tsi. Liquid-phase sintering was carried out in vacuum at temperatures which depended on the chemical composition of the system involved, but which were usually around 2640° F. The resultant materials had a density approaching 100 pct of theoretical. The

Jan 1, 1961