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By J. E. Hove

The high temperature physical properties of graphite are reviewed and interpreted in the light of present day knowledge of the mechanisms affecting these properties. The thermal and mechanical behaviors only are discussed and, whenever possible, comparisons are made with other refractory materials. Possible further studies are indicated, including some carbide work. AS long as the term high temperature implied only temperatures up to about 1000°C, the materials problems which arose could usually be handled by fairly conventional metal alloy types, such as the Co-Cr-Ni superalloys, for which there exists a great deal of technology. Perhaps this temperature can still be considered an upper limit for normal applications, but it is certainly true that the number of abnormal applications is increasing rapidly. The advent, in recent years, of ram-jet and rocket missiles and of high power nuclear reactor heat sources has raised a host of questions concerning the basic problem of what material to use in the temperature range up to 2000°C and higher. While there are, of course, many metals, in the second and third transition series, which melt at considerably higher temperatures than this, these metals are, at present, pretty well excluded from practical use by other considerations, such as re-crystallization, chemical activity, or excessive plastic deformation. The behavior of metals, from the standpoint of dislocation theory, is just beginning to be understood and thus there is some hope for the future development of very high temperature metals, but the immediate problems would most logically appear to have solutions involving the nonmetals, such as the refractory ceramics and graphite. For this reason, there is presently a great deal of engineering and experimental research being performed on the latter materials, much of this research being exploratory in the sense of gathering new property data. The situation, so far as graphite is concerned, is somewhat more fortunate than with the other refractory solids in the sense that a great deal is already known about its basic properties. This stems both from the fact that the carbon-carbon bond has been of interest to chemists for a long time (and graphite can be considered as a very large aromatic molecule, if desired) and the fact that its properties, both as a function of temperature and of radiation damage, are of critical importance to nuclear reactor designers. It is still true, of course, that such fundamental questions as why graphite remains solid to such a high temperature and why it has such a high thermal conductivity cannot entirely be answered at the present time. It is, nonetheless, meaningful and instructive to consider such problems in the light of existing knowledge. This is what the present paper will attempt to do. Before going on, it may be appropriate to classify graphite and justify its discussion before readers primarily interested in metals. Graphite is comparatively unique among materials in that there is always a property or group of properties which precludes calling it either a metal, a semiconductor, or a ceramic. It has the high electrical and thermal conductivities of a metal, but the artificial, poly-crystalline types show a negative thermal coefficient of electrical resistivity, generally characteristic of semiconductors. On the other hand, semiconductors, by definition, show an ever increasing resistivity as the temperature is lowered, whereas graphite approaches a finite, and, indeed, a rather low resistivity in the region of 10°K and, furthermore, a good single crystal of graphite has a positive temperature coefficient, as for a metal.' On still another hand, its porosity and brittleness at lower temperatures would put graphite in the ceramic class although, unlike most ceramics, it is readily machinable and has a high resistance to thermal shock. All things considered, it is probably more nearly appropriate to call graphite a metal than anything else. Although certainly outstanding in some ways, graphite has its peculiarities and, especially if the reader is unfamiliar with the data, it is probably valuable to review some representative property variations at high temperature. This review is meant to be mainly illustrative and no attempt has been made to be exhaustive. Review of High Temperature Properties At ordinary pressures, graphite does not melt, but sublimes directly into the gaseous phase at about 3700°C. Although the phase equilibrium diagram is still in some doubt, graphite will melt, at a slightly higher temperature, at pressures in excess of about 100 atm. The chief difficulty of using graphite in an oxidizing atmosphere is that the reaction rate becomes quite high at fairly low temperatures. If a threshold oxidation temperature2 is defined as the temperature at which graphite loses 1 pet of its weight in 24 hr, the value in air is 450°, the value in steam is 700°, and the value in carbon dioxide is 900°C. Efforts are presently being made to raise this threshold temperature either by impregnation with a retardant of some type (sodium tung-state and phosphoric acid, for example) or by a suitable metal or oxide coating. It is probably fair to say that, to date, these attempts have not shown any outstanding success in all respects. Most commercial graphites are fabricated by impregnating a carbon flour (say of coke or lampblack particles) with some type of hydrocarbon

Jan 1, 1959

By R. M. Brick

THE Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic prob-lems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segrega-tion. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute con-centration, with a resultant normal segregation or coring effect during freezing. Theoretically, diffusion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions alumimum-copper alloys segregate inversely and aluminum-magnesium alloys segre-gate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937

By Carle Hayward

IN reheating quenched steel to remove part of the hardness, the softening effect has generally been considered to be a function of temperature and time. The temperature effect is well known, and long before pyrometers were heard of the blacksmith was able to do a good job of tempering, by rule-of-thumb methods and experience in judging temperatures. Modern conditions, which demand steel that will withstand the severest tests, require that the heat treatment he carried out with every possible precaution to secure the best results obtainable. Pyrometers and heat-treatment furnaces of many types are on the market and improvements are continually being made so that it is now possible to regulate the temperature in heat treatment very accurately. There is -still a question regarding the time that the steel should be subjected to treatment. It is customary with all operators to insure the desired tem-pressure throughout the specimen and it is generally supposed that a longer treatment of a hardened steel produces a further softening but there are few published figures showing the exact effect of time of treat-ment at constant temperature. A search of the literature disclosed several brief statements that the tempering effect was a function of both time and temperature, but in no case were any figures given. The opinion is very generally held that the well-known tempering colors are accurate indicators of the degree of tempering. This is disputed by Brearley (The Heat Treatment of Tool Steel, page 102) who states: It has been said that the result would be the same in respect to both hardness and other properties whether the colors were obtained by a shorter heating at a higher temperature or a longer heating at a lower one. This, to say the least, is a very doubtful conclusion, and is certainly not borne out by mechanical tests on oil-hardened and tempered motor car steels, which, after tempering for periods varying from 15 min to 2 hr., show no very great differences. The present investigation had for its object the obtaining of some definite data regarding the effect of time, which might serve as a guide to those engaged in the heat treatment of steel. The Rhode Island Tool Co. cooperated by furnishing the steel and machining the test specimens.

Jan 2, 1917

By W. S. Potter

The proportions of manganese and carbon in manganese steel are familiar to all…

Jan 1, 1915

By A. P. Watt

Foreword...............................................................323 Location of District..................................................... 324 Geology and Mining..................................................... 325 Topography and Climate................................................. 325 Lcad Production of the District...........................................325 Operating Companies in Southeast Missouri................................ 327 History of the District................................................... 329 Present Method of Treating the Ore....................................... 335 Character of Ore Treated...........................................338 Chemical Analyses............................................. 339 Description of Polished Specimens.................................340 The Concentration Problem of the District............................. 341 Handpicking at Mine La Motte....................................... 343 Crushing............................................................344 Roll Practice in the District.......................................... 346 Screening Practice................................................... 347 Jigging the Ore..................................................... 347 Bull Jigging.................................................... 348 Hancock-jig Practice............................................ 348 Classification of the Ores.............................................. 350 Table Treatment....:............................................... 352 Regrinding of Middling.............................................. 354 Description of Marathon Mill..................................... 358 Results of Preliminary Tests.....................................359 Rod Wear in the Marathon Mill.................................. 367 Steel Consumption.............................................. 368 Design of Marathon Mills.............. :......................... 368 Treatment of Table Middling........................................ 368 Slime Concentration................................................. 370 Methods Used in the Past.......................................370 Present Methods of Treatment................................... 371 Flotation of Slime.......................;........................ 371

Jan 1, 1918

By W. C. Winegard, C. Feng, C. Elbaum

SEVERAL investigations have been made concerning the effect of oxygen on the mechanical properties of titanium 1-6= In particular, the yield strength has received considerable attention. Finlay and snyder2 report a 0.2 pet strain offset yield strength if 49 kg per sq mm in titanium containing 0.1 pct 0 and 61 kg per sq mm in titanium with 0.2 Pct 0. These results are in good agreement with those of Jaffee, Odgen, and Maykuth3 who report values of yield strength

Jan 1, 1960

By D. Turnbull, R. E. Cech

Small particles, 10-20 microns diameter, of a 28.6 atom pct nickel, balance iron alloy, have been supercooled 186 C with respect to bulk alloy M, temperature. Particles exhibit a marked mechanical shock sensitivity while being held in a supercooled state. The tendency for shock to induce martensitic transformation appears to be a maximum at —140 to —160°. Slow cooling of particles in mechanical contact with one another results in extensive martensite formation. This is prob-ably the same effect as the catalytic effect observed in polycrystals where martensite formation in one grain induces transformation in other grains. AS a result of extensive research over the past decade on the martensitic transformation, a much better though not complete understanding of the transformation has resulted. Recent reviews by Bilby and Christian' and Kaufman and Cohen2 have

Jan 1, 1959

By Norman P. Goss

What would appear to be a very simple process on paper has proved to be overrun with a multitude of unseen difficulties. For more than 70 years attempts have been made to cast metals in a continuous manner, but it has been only within the last Io years that some degree of success has been achieved.1 Historical Development Bessemer's Experiments—Method I Bessemer was the first to try to cast molten metal in a continuous manner. His method is fully described in U. S. Patent No. 49053, issued in 1865. The patent drawing is shown in Fig. I. In this method the molten metal was poured between a pair of rolls of large diameter, which were cooled by water sprays. Means were provided to prevent moisture from coming into direct coptact with the molten metal. The width of the strip was controlled by the flanges. On paper this should work to perfection, but it is beset with many difficulties still awaiting solution. Bessemer failed to reduce his invention to commercial practice. About 1890 Bessemer's method was revived by Norton and associates (U. S. Patent No. 441375). They formed the Fluid Metal Rolling Co. at Maywood, Ill., and spent $250,000 in endeavoring to develop the technique for this simple method. Finally they had to abandon it. Naturally, they did carry the technical development far beyond anything Bessemer had done, but even so it was far from being a useful commercial success. In recent years it has undergone further development by C. W. Hazelett (U. S. Patent No. 2058447), who has succeeded in obtaining long lengths of copper, brass, aluminum, and even stainless steel. He introduced many' ingenious devices but the greatest obstacle still remained—the disintegration of the roll surface when the surface is heated and chilled in rapid succession. Difficulty is also experienced in maintaining a uniform supply of molten metal to the rolls. The patents pertaining to this method would indicate these to be the major obstacles. Experimental work by Mellen—Method 2 A departure from the method introduced by Bessemer, was tried by Grenville Mellen, of East Orange, K. J., sometime between 1914 and 1920, who obtained a number of patents.2 His method is illustrated in Fig. 2. This method failed to make an impression upon the art; however, it is of value in pointing out the difficulties the inventor ran into and the way in which he tried to meet them. The split mold sections form two endless chains. When going through the center of the apparatus, these sections engage each other to form a complete mold. As the engaged mold section moves downward at a constant speed, molten metal is teemed into it. As this is going on, another set of cooperating mold sections move into position on top of the one being filled. The molten metal is teemed into the mold through a silica tube. According to the teachings of this patent, the level of molten

Jan 1, 1945

By Alfonso Merlini

DIFFERENT explanations have been given by the two current theories of the annealing textures for the variation of annealing texture with the annealing temperature observed in rolled polycrystal-line aluminum,' copper,2 and brass, And in rolled single crystals of copperk and silicon iron.' The theory

Jan 1, 1957

Jan 1, 1961

By H. C. Rogers

It has been shown previously'- 3 that when a mild steel or iron is charged with hydrogen, the normally observed yield point is eliminated or considerably

Jan 1, 1960

Jan 1, 1969

By B. J. Nelson, F. N. Rhinos

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a' continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By F. N. Rhinos, B. J. Nelson

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a' continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By C. Z. Serpan, L. J. Wittenberg

The density of liquid plutonium was determined, by a pycnometm'c technique, from 664 to 788°C and exhibited a temperature dependence, which could be expressed as:. P= C17.63 - 1.52 x 10-"t] +0.04 g per cc where t = OC. These density values compare favorably with the values previously obtained by a technique utilizing Archimedes' principle. The apparatus and method were evaluated when the densities 0.f molten tin and bismuth were measured and found to be in agreement with accepted literature values. PLUTONIUM or an alloy of plutonium in the liquid state has been proposed as a fuel for a fast-breeder type nuclear power plant.' Since knowledge of the liquid density of plutonium is required for the proper design of such a system, this study was undertaken. In addition, the density and volume expansion coefficient of liquid plutonium are of interest for comparison with these same properties of the six allotropic modifications of the solid metal. Comstock and GibneyZ were first to report a value for the density of liquid plutonium. The value for only one temperature, 665"C, was calculated from data obtained by the radiography of the meniscus, Fig. 3. Recently, the density at a series of temperatures has been reported by Knight,3 who obtained his values by using a differential volumeter, and by 01-sen, Sandenaw, and Herrik, who obtained their values from measurements of the loss in weight of a tungsten bob immersed in the liquid. The density of liquid plutonium reported here was determined by a vacuum pycnometer method. In an evacuated system, the tips of calibrated tantalum pycnometers were lowered beneath the liquid sur-

Jan 1, 1962

By G. A. Alers, J. H. Bechtold, R. W. Armstrong

The plastic flow of .molybdenum was studied in compression at temperatures below the ductile-to-brittle transition in tension. It was found that molybdenum is ductile in compression at all temperatures down to —196°C. The yield strength continues to increase with decreased test temperature below the tensile ductile-to-brittle transition temperature range. Difficulty was encountered in correlating the experimental data obtained with existing theories of plastic flow. THE body-centered-cubic metals as a group show a rapid and very large increase in yield strength with decreasing test temperature.' It is of fundamental importance to the understanding of the mechanism of plastic flow that this general characteristic be examined carefully. Unfortunately, brittle fracture in low-temperature tensile tests prohibits the measurement of flow properties at very low temperatures. By using compression tests, fracture can be suppressed and the plastic flow of the bcc metals can be studied far below their tensile ductile-to-brittle transition temperatures. Molybdenum was chosen for this experiment and plastic-flow data were obtained down to —196°C.

Jan 1, 1959

By Larry Kaufman, Morris Cohen

THE solid phase equilibria' and the martensitic transformation in the iron-nickel system have been the subject of considerable study. In addition, there have been numerous investigations on the calorimetric and thermodynamic properties of iron-nickel alloys. The purpose of the present work is to extend the existing information concerning the martensitic reaction in the iron-nickel system, and to develop a general thermodynamic treatment which will encompass the equilibrium and non-equilibrium phase

Jan 1, 1957

By N. Christensen, B. Augland, T. H. Johansen

Samples of an Fe-Nb alloy were brought to equilibriurtr with hydrogen-methane mixtures in the temperature range from 950° to 1050°C, and subsequently analyzed on their carbon contents. The solubility pvoduct L = [%Nb] [%C] may be represented by the equation Approximate solubilities indirectly assessed through hardness measurements have been included from a previous report. These data are shown to be in a fair agreement with the present solubility measurements. IN an investigation based on hardness measurements by de Kazinczy, Ms, and pachleitnerl the molal heat of solution of NbC was estimated to 11.5 kcal per mole. This value was considered rather small, and an investigation using a similar technique was carried out. The results indicated a heat of solution about 35 kcal per mole.2 At this stage it was decided to determine the solubility under conditions of true equilibrium . During the course of this work a similar investigation was published by Smith. 3 His heat of solution, 41.6 kcal per mole, is not very different from the value resulting from the present work (42.5 kcal per mole). Our solubility product, on the other hand, is at considerable variance with that reported by Smith. Possible reasons for these differences are discussed below. Mori, Tokizane, and saheki 7 have studied the behavior of niobium in commercial steels, with special attention to the formation of niobium carbide, nitride, and sulfide. Assuming a carbide composition Nbco.87 based on X-ray diffraction and chemical analysis of residues extracted from Fe-Nb-C-S alloys, the molal heat of solution of niobium carbide was estimated to 35.2 kcal per mole. MATERIALS AND EQUIPMENT The chemical analysis of the materials is given in Table I. Electrolytic iron* was used in the preparation of

Jan 1, 1968

By R. L. Vaughn, H. R. Cooper

Effective procedures for automating X-ray assaying by use of a computer are described. These methods have advanced the reliability and accuracy of X-ray data, resulting in improved assay measurements for operations and process control. Assaying by X-ray fluorescence has been increasingly used in the mining industry, both for analyzing solid H.R. COOPER and R.L. VAUGHN, Members AIME, are Systems Manager-Process Control and Senior Systems Analyst, respectively, Scientific & Engineering Computer Center, Ken-necott Copper Corp., Salt Lake City, Utah. TP 68B236. Manuscript, Sept. 16, 1968. Discussion of this paper, submitted in duplicate prior to Dec. 15, 1969, will appear in SME Transactions, March 1970, and AIME Transactions, 1970, Vol. 247. samples for smelter, mill, and mine quality control and for continuous stream analysis of mill pulps. The important advantages of X-ray methods in laboratory assaying are reduced analysis cost, and for on-stream analysis, immediate assay information on concentrator streams. Of the numerous reports concerning X-ray analysis in mining operations, one is referenced which can be noted particularly in conjunction with this report.' Continuous X-ray analyzers have been installed at Kennecott and other mining companies for operations guidance and trend information for a number of years. However, complete operational acceptance of X-ray data has been slow, due* to the difficulty in maintaining

Jan 1, 1970

By Nicholas J. Grant, Raymond E. Cairns

A high-purity chromium, made by solid-state extrusion, and a series of molten, extruded, dilute alloys containing carbon, oxygen, nitrogen, and sulfur were studied to establish the effects of composition, cooling rate, grain size, strain rate, and prior strain on the transition temperature for brittle THE transition from ductile to brittle fracture with decreasing temperature remains of extreme interest especially among the refractory metals, such as tungsten, molybdenum, and chromium, which have relatively high transition temperatures. Fracture, yield stress, and hardness. Tension tests at a strain rate of 0.015 per min were generally utilized. Results are interpreted in terms of the quantity of each element retained in solid solution. Of these elements, chromium has been studied the least, but deserves additional attention because of its superior oxidation resistance for high-temperature use. In the past, impurity elements which have received attention are carbon, nitrogen, oxygen, and sulfur;'-' of these, nitrogen has usually been considered to be the most detrimental. Unfortunately, because of different levels of both specific and total impurity content, and because of the many different test and evaluation techniques used, a clear, definitive picture of brittle fracture in chromium has not been forthcoming. However, many

Jan 1, 1964