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By T. Egleston

The necessity of using a refractory material capable of much greater resistance to chemical action and having a far higher melting-point than those which contain silica, which melt and sweat off in the furnace even when not exposed to bases forming with silica more or less fusible compounds, has led to a careful practical study of all those materials which contain very refractory bases. The results of these researches, extending over several years, and made on a very large scale in many of the largest works in Europe, are of the highest interest, not only considered as a step in the progress of the study of the materials themselves, but in the application of refractory materials to metallurgical uses in general. The result of the experience of the last seven years with these basic materials, as in general with all such substanccs, is that natural products cannot be used as such. They are either too uncertain in their quality, contain substances which may in certain cases be very injurious, or, when in a condition in which they might be used, are so rare as to become practically unavailable for employment on a large scale. The materials that may he used are therefore not only limited in number. but they must be prepared artificially. When the use of basic artificial material is further extended, no doubt the number of these substances will not only be greatly increased, but the methods of preparation will be both perfected and cheapened to such an extent as to permit their application in processes for which they have hitherto proved too expensive. The quantity of refractory materials required for making ingots will he from 130 to 150 Ibs. per ton, or between 6 and 8 per cent. of the metal produced. In an establishment producing 2000 to 3000 tons of steel per week, considerable space is required to handle the basic materials properly. It is proposed in this paper to briefly discuss these basic materials and their application in the only two metallurgical processes where they have as yet been applied. These are the basic Bessemer and the basic open-hearth process, known as the Thomas-Gilchrist processes.

Jan 1, 1886

By R. W. Gurry

WHEN a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, vet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. EXPERIMENTAL PROCEDURE Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;1 it suffices to state here that the carburization lasted about 140 hr. at 760°C. (1760°F.) and 44 hr. at 1110°C. (2030°F.), these periods being long enough-on the basis of the calculations presented later-to ensure that the specimen was about 9.99 per cent saturated at each temperature. The speci¬men was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully [carburized] specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By G. Sachs, L. J. Ebert, W. F. Brown

IT is a generally recognized fact that a steel quenched from the austenitic range and tempered to yield a structure composed of tempered martensite becomes increasingly more ductile with increasing tempering temperature. However, the conventional tensile test fails to yield any value that is sensitive to differences in behavior on tempering among the various low-alloy steels or among different heats of a particular steel. The notched impact bending test, on the other hand, has been recognized for a considerable length of time as capable of revealing differences in impact properties among various steels tempered to the same strength level (i.e., the same tensile strength in a conventional tensile test), However, this test is very complex and its significance has not been clarified up to the present time. Of its three characteristic features-the high speed, the notch, and the bending-the notch has been found by Davidenkov2 to be the most potent embrittling factor. Recent investigations on low-alloy steels3,4,7,8 have shown static notch-bar tensile tests to be more lucid and to evaluate the metal properties in much the same manner as impact tests, In an attempt to analyze the fundamental nature of this test,8 it was found possible to separate the effects of the two basic characteristics of the stress pattern introduced by the presence of a circumferential notch, the stress state and the high initial stress concentration at the notch bottom, The major conclusions drawn from these previous investigations were as follows: I. The magnitude of the triaxiality at fracture depends primarily on the initial notch depth. Its effect is a great reduction in the average ductility (contraction in area at fracture in the notched section) as compared with that observed in uniaxial tension, This triaxial stress state occurs at a point in the interior of the notch specimen, It determines the notch ductility if the notch is mild and/or the metal possesses a considerable ductility. On the contrary, brittle specimens probably fracture on the metal surface (at the notch bottom) at which point biaxial stress state is present, This biaxiality also considerably reduces the ductility of the metal. For small notch ductilities the notch strength and the notch ductility become very sensitive to embrittling factors, This is contrary to the behavior of the ductility values derived from a conventional tensile test, which are comparatively insensitive.

Jan 1, 1946

By William Firmstone

ON the 19th December, 1833, a patent was granted to F. W. Geisenheimer, for smelting iron ore with anthracite. In his claim he says: "Sixthly, though I cannot, and do not, claim am exclusive right of the use of heated air, for any kind of fuel, nevertheless I believe to have a right to claim the use of heated air, applied upon, and in connection with, the said principle and manner discovered by me, to smelt iron ore in blast-furnaces with anthracite coal, by applying a blast of air in such quantity, velocity, and density, or under such pressure, as the compactness, or density, and the continuity of the anthracite requires, as above amply and fully described and illustrated." Dr. Geisenheimer made experiments in smelting iron ore with anthracite at the Valley Furnace, near Pottsville, but he failed to carry out to good practical results the principles enunciated in his patent. In the Journal of the Franklin Institute for February, 1838, a communication was published that was made by Mr. George Crane, of the Yniscedwyn Iron Works, South Wales, to the British Association, in September, 1837. On the smelting of iron with anthracite coal, Mr. Crane states therein, that he began the use of an¬thracite with hot-blast on the 7th February, 1837, in a cupola blast-furnace, 41 feet high, and 10' feet across the boshes ; product, 34 to 36 tons a week. Mr. Crane goes on to say, "It may not be uninteresting to be informed in what matter the idea first occurred to me of applying a heated blast to anthracite coal. One evening, after I had placed a piece of it upon my parlor fire (which had before been made up with bituminous coal), and had allowed it to arrive at a red heat, upon applying as fierce a blast to this piece of coal as I could raise from a pair of bellows, I noticed a black spot or mark

Jan 1, 1875

By C. B. Sclar and

A graphical solution is presented for the equation v =v &-cU where vb is the volume of liquid b of density 6 that must be added to liquid a of volume va and density d, in order to obtain a heavy-liquid solution of preferred density dm for mineral fractionation. The equation is valid only for pairs of liquids whose volumes are additive, but empirical density-composi-tion data show that this condition is met over wide compositional ranges by all of the heavy solutions that are commonly used for mineralogical analysis. The chart is a nomograph which consists of two horizontal volume scales ad a vertical density scale arranged so that one volume scale occurs on each side of the density scale. All the scales are linear. For two liquids of density d, and &, respectively, each volume scale has an independent level on the density scale, ad the graphical solution for vb on the nomograph is obtained by construction of one straight line. The chart can be prepared easily to cover any density range with any desired accuracy by proper selection of the scales. Heavy-liquid separation of particulate samples is an indispensable analytical procedure in the mineralogical and mineral-process ing laboratory. Heavy liquids may be used 1) to isolate specific minerals in the form of high purity products or to fractionate samples into several products with density limits for petrographic, chemical, spectrographic, and X-ray diffraction analysis,'-' 2) to determine the density of minerals,'-l4 3) to facilitate the recognition and identification of optically similar associated minerals,15 and 4) to determine quantitatively the degree of liberation of ore minerals in ores and mill products at various limiting sizes." The preparation and recovery of heavy liquids suitable for mineralogical analysis are discussed fully in the literature and operational procedures and special equipment for heavy-liquid separation are described in numerous references.'747837' 13,18,25-42 Useful tabulations of heavy liquids for mineralogical analysis are given by Tickell, Mil-ner,' Twenhofel and Tyler,' and Lange and a very complete up-to-date list of minerals arranged according to increasing density is given by Mursky and Thompson. USEFULNESS OF THE DENSITY CHART For any particulate sample, the limiting densities selected for its fractionation by means of heavy- liquid separation depend on the respective densities of the constituent minerals and the specific objectives of the separation. In many instances, the densities of readily available and practicable heavy liquids do not coincide with those that are required, and suitable liquids of the proper density are obtained by dilution with miscible liquids. In the general case, one may wish to mix either a pure liquid (A) or a solution of two miscible liquids (AP,,) of known density with either a pure liquid (B) or a different solution of the two miscible liquids (A,B,) of higher or lower density in order to obtain a final liquid of the preferred density. In conventional practice, the latter is reached empirically by trial-and-error addition of increments of one liquid to the other. The density of the final solution may be determined either by accurately weighing a known volume of the final liquid,'' 532;4;40, or by means of I)a Westphal balance, 2)a hydrometer, a refractometer in the case of binary liquid systems for which density-refractive index data are available,15 4) natural or synthetic .indicators of known density, a pycno-meter. Like all trial-and-error methods, these procedures are time consuming and many require special equipment which may not be available, The purpose of this paper is to show that the volume of a liquid of known density which is to be added to another liquid of known volume and density in order to obtain a solution with an intermediate preferred density may be determined rapidly and accurately by a graphical method provided that the two liquids form ideal or quasi-ideal solutions whose volumes are additive. Empirical data47'8~'8~4B'49 show that solutions prepared from pairs of miscible

Jan 1, 1961

By John S. Johnson, Thomas Fraser

SIZING is the process of separating mixed particles into groups of particles all of the same size, or into groups in which all particles L range between certain definite maximum and minimum sizes. In coal preparation, sizing is generally accomplished by passing the coal over screens. Separation by differential settling in air or water currents has been adapted to the special field of separating very fine sizes, and these processes are in commercial use to a relatively small extent in the coal industry. Separation with screens is a very old industrial practice. Agricola 1 described the use of screens for ore treatment in the middle ages. In the literature of the British coal industry references were made to the screening of coal as early as 1589, but the practice of extensive sizing for the market did not become general until the last half of the nineteenth century. In America, the practice of sizing developed first in the Pennsylvania anthracite region, beginning with the use of rakes2 in the mine working places to recover coarse coal. This mining procedure left the fines in the mine. Preparation outside the mine started with the installation of stationary cast-iron plates with 4 to 6-in. square holes. The run-of-mine coal was dumped upon the platforms, the large pieces of rock were picked out by hand, and the large lumps of coal were broken with hammers. The term "breaker," which still applies to the anthracite-preparation plant, originated with this practice, but the term is no longer descriptive of the entire function of the plant. In 1884, the first power-operated anthracite coal breaker3 was erected by Gideon Bart at his colliery at Wolf Creek near Minersville, Pa. This plant utilized a system of rolls for breaking the coal and revolving screens for sizing. The plant was driven by a steam engine. It could handle

Jan 1, 1943

By Walter W. Bradley

AT ONE TIME OR ANOTHER and in greater or less amounts, gold has been mined in at least 40 of California's 58 counties. It may not be inappropriate, by way of introduction, to give a brief historical statement relative to her production of the yellow metal. The presence of gold in the gravels of San Gabriel, San Francisquito, and other streams near Los Angeles, was known and they were worked in a small way by the Indians, at least as early as. 1841' and possibly 1820. -On March 2, 1844, Don Manuel Castanares, deputy for California to the Congress of Mexico, reported' to his government that placers near Los Angeles had yielded up to December, 1.843, a total of 2000 oz. of gold dust, most of which had been sent (via Mexico) to tile United States Mint at Philadelphia.

Jan 1, 1932

ALABAMA Aldrich.-Lloyd, T. W. Anniston.-Carrington, F. G. Klugh, B. G. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson V. Salmon, h. S. Stuart, Q. W. Birmingham.-Adams, J. H. Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W. Armstrong. W. D. Ball, E. M. Bonnyman, J. Bush, M. W. Carter, E. Crawford, G. G. Davis, C. B. Dryer. T. B.

Jan 1, 1923

NAME "Utah" is derived from the name of the Indian tribe, variously spelled "Yuta," "Ute," "Youta." "Uta." "Eutaw," and finally "Utah." It means "in the tops of the mountains," or "on the heights." The state emblem is the "Beehive," typical of industry. State nickname is "Beehive State." AREA Utah is the tenth state in area. It contains 84.990 square miles, of which 2.806 miles are water. When admitted as a territory in 1850. Utah included all the area from the east line of California to the summit of the Rocky Mountains between the 37th and 42nd parallels, which embraced practically all of the present state of Nevada, all of western Colorado, part of Idaho and part of Wyoming, in addition to the present area of Utah.

Jan 1, 1925

By Gerald Sherman

MINING asbestos ore by caving at Thetford Mines, Quebec, has been described in the Transactions of the Canadian Institute of Mining and Metallurgy in papers presented by the staffs of The Asbestos Corp. Ltd., in 1934, and Johnson's Co. Ltd., in 1941. The production by caving prior to 1949, in round figures, has been 14,500,000 tons of ore by The Asbestos Corp. and 5,500,000 by Johnson's Co. They are the only caving operations in asbestos at the present time. The Jeffrey mine of the Canadian Johns-Manville Co. at Asbestos, 40 miles southwest of Thetford, is well along in preparations for caving, and The Bell Asbestos Mines Ltd. at Thetford Mines, will follow their examples later. GERALD SHERMAN, Member AIME, is Consulting Engineer, Johnson's Co. and Canadian Johns-Manville Co., New York, N. Y. AIME San Francisco Meeting, Feb. 1949, and New York Meeting, Feb. 1950. TP 2828 A. Discussion (2 copies) may be sent to Transactions AIME before May 31, 1950. Manuscript received Nov. 2, 1949. Nearly all of the asbestos produced by the western hemisphere is mined in those districts of Canada. Since it has been the subject of a number of technical papers, this contribution is offered as a review of progress. Some introductory information seems appropriate, for few members of the American Institute of Mining and Metallurgical Engineers are familiar with the mineral, or how asbestos deposits differ from others in caving characteristics. Asbestos is found in peridotite, a basic intrusive rock irregularly altered to serpentine and erratically fractured, well enough to cave in bulk, but leaving many blocks of solid ore of all sizes scattered through the deposit. Chrysotile is the variety of asbestos produced in Canada. Its fibers are the most valuable commercially, having a good proportion of long fibers, strong, silky, flexible, and suitable for spinning. The fibers occur in all lengths, from the microscopic to 3 in., or more, the shorter are more abundant. Their values depend on length combined with other qualities noted above. They occur as veinlets filling fissures in the peridotite, with crystals compactly arranged in parallel across the cracks. They are sometimes lightly frozen to the walls but the partings are distinct, often marked by particles of magnetite adhering to the fiber ends. Sometimes they break away from the rock in slabs an inch or more in thickness. In wide fissures the fibers are not always continuous, the "broken fibers" being separated by lines of parting with occasional scattered grains of magnetite, which is an injurious mineral to be elirninated when possible. In addition to the chrysotile ''Cross fiber," some "slip fiber" is found in fault fractures in limited quantities of less valuable character. With the exception of the Asbestos Corp, ore, in which the content is said to be more uniform, asbestos is eccentrically distributed through the peridotite. It is the general impression that the higher grades are more often found in hard rock. There are rich pockets and leaner areas which range down through various grades to minor barren sections. Wholesale mining is necessary to make sure of recovering all the high grade for there are no reliable indications of its existence. Ore selection only appears in constructing assay-grade limits for caving. The mill yield of the Thetford ore body in 1934 was 6 to 10 pct of the ore milled, made up of all classes, with occasional runs up to 15 pct or so. Quotations for Canadian asbestos* are as follows: Per Ton No. 1 Crude (% in. and longer) $896 @ $960 No. 2 Crude (Y8 to % in.) 350 @ 545 Spinning (less than % in.) 204 @ 378 Other classes, price diminishing with length. Shorts or "refuse" 24 @ 46 • From Eng. and Min. Jnl., Nov. 1948. Asbestos of even superior quality for electric insulation is found in Arizona limestone. It is white, containing very little combined iron, but occurs only in small quantities.

Jan 1, 1951

By Gerald Sherman

MINING asbestos ore by caving at Thetford Mines, Quebec, has been described in the Transactions of the Canadian Institute of Mining and Metallurgy in papers presented by the staffs of The Asbestos Corp. Ltd., in 1934, and Johnson's Co. Ltd., in 1941. The production by caving prior to 1949, in round figures, has been 14,500,000 tons of ore by The Asbestos Corp. and 5,500,000 by Johnson's Co. They are the only caving operations in asbestos at the present time. The Jeffrey mine of the Canadian Johns-Manville Co. at Asbestos, 40 miles southwest of Thetford, is well along in preparations for caving, and The Bell Asbestos Mines Ltd. at Thetford Mines, will follow their examples later. GERALD SHERMAN, Member AIME, is Consulting Engineer, Johnson's Co. and Canadian Johns-Manville Co., New York, N. Y. AIME San Francisco Meeting, Feb. 1949, and New York Meeting, Feb. 1950. TP 2828 A. Discussion (2 copies) may be sent to Transactions AIME before May 31, 1950. Manuscript received Nov. 2, 1949. Nearly all of the asbestos produced by the western hemisphere is mined in those districts of Canada. Since it has been the subject of a number of technical papers, this contribution is offered as a review of progress. Some introductory information seems appropriate, for few members of the American Institute of Mining and Metallurgical Engineers are familiar with the mineral, or how asbestos deposits differ from others in caving characteristics. Asbestos is found in peridotite, a basic intrusive rock irregularly altered to serpentine and erratically fractured, well enough to cave in bulk, but leaving many blocks of solid ore of all sizes scattered through the deposit. Chrysotile is the variety of asbestos produced in Canada. Its fibers are the most valuable commercially, having a good proportion of long fibers, strong, silky, flexible, and suitable for spinning. The fibers occur in all lengths, from the microscopic to 3 in., or more, the shorter are more abundant. Their values depend on length combined with other qualities noted above. They occur as veinlets filling fissures in the peridotite, with crystals compactly arranged in parallel across the cracks. They are sometimes lightly frozen to the walls but the partings are distinct, often marked by particles of magnetite adhering to the fiber ends. Sometimes they break away from the rock in slabs an inch or more in thickness. In wide fissures the fibers are not always continuous, the "broken fibers" being separated by lines of parting with occasional scattered grains of magnetite, which is an injurious mineral to be elirninated when possible. In addition to the chrysotile ''Cross fiber," some "slip fiber" is found in fault fractures in limited quantities of less valuable character. With the exception of the Asbestos Corp, ore, in which the content is said to be more uniform, asbestos is eccentrically distributed through the peridotite. It is the general impression that the higher grades are more often found in hard rock. There are rich pockets and leaner areas which range down through various grades to minor barren sections. Wholesale mining is necessary to make sure of recovering all the high grade for there are no reliable indications of its existence. Ore selection only appears in constructing assay-grade limits for caving. The mill yield of the Thetford ore body in 1934 was 6 to 10 pct of the ore milled, made up of all classes, with occasional runs up to 15 pct or so. Quotations for Canadian asbestos* are as follows: Per Ton No. 1 Crude (% in. and longer) $896 @ $960 No. 2 Crude (Y8 to % in.) 350 @ 545 Spinning (less than % in.) 204 @ 378 Other classes, price diminishing with length. Shorts or "refuse" 24 @ 46 • From Eng. and Min. Jnl., Nov. 1948. Asbestos of even superior quality for electric insulation is found in Arizona limestone. It is white, containing very little combined iron, but occurs only in small quantities.

Jan 1, 1951

By Edgar C. Bain, William E. Griffiths

The results of an inquiry into the structural nature of some 70 iron alloys containing both nickel and chromium over a considerable range of concentration are briefly described in this paper. This study is a part of a comprehensive program of investigation into alloys involving chromium in progress at the Union Carbide and Carbon Research 1aboratories. All the compositions studied contained carbon in amount comparable to commercial alloys. The B Constituent In addition to locating the limits of composition for the three principal types of structure (polyhedral ferrite, martensite and austenite) and their combinations, certain other features of the system were observed. A hitherto undescribed brittle constituent (designated here as the "B constituent") was discovered. It is very hard, non-magnetic and forms in two modes from chrome-ferrite by recrystallization. It is the stable low-temperature condition for the equal-proportion chromium-iron materials containing less than 10 per cent. nickel. Although it partakes of the nature of an inter-metallic compound, yet it may exist over a considerable range of composition. It is non-existent above a temperalure zone, varying with composition, from 800° C. to 950° C., and heating above this critical temperature develops chrome ferrite persistent after average cooling rate; a few hours just below this temperature will develop the complicated brittle crystalline type. The B constituent, when found in the grain boundaries of alloys of lower chromium content, contributes a serious brittleness removable, however, by heating and cooling rapid enough to prevent its re-format'ion. By suitable means of precipitution, the hard B constituent can be made to strengthen the already stiff alloy matrix in the manner of submicro-scopic particles, as exemplified in duralumin or the Sykes iron-tungsten and iron-molybdenum alloys. A possible explanation is offered for the familiar brittleness developed in chrome iron at temperatures above about 475" C. and removable by

Jan 1, 1927

By J. B. Morrow, D. H. Davis

THERE are two general approaches to the problem of increasing profits from an operation. One is to lower expense; the other is to raise income. Mechanical preparation of coal may be used for either purpose but a prudent consideration of many details must precede any decision lest the results be negative instead of positive. It is quite possible that any net gain will result from a combination of the two. Since mechanically prepared coal invariably is a better product qualitatively than a hand-picked coal from the same mine, it is a reason- able expectation that the customer will be willing to increase the producer's income by paying a higher price. Or there may be the possibility that a combination of mechanical mining plus mechanical cleaning will give a lower over-all production cost for the coal in the railroad car. More likely, there will be found a combination of these two factors. From the customer's point of view, the competitive delivered cost per B.t.u. considered in relation to such incidental factors as dust nuisance, handling properties, ash disposal, and ash fusibility determines what he will pay. In a bulk tonnage product such as coal, freight is a very considerable part of the delivered fuel cost, and obviously freight paid on incombustible ash has no economic attractions. INCENTIVE FOR CLEANING Coal is prepared in four major ways: 1 (I) by screening or sizing, (a) by mixing or blending, (3) by cleaning, including hand picking and mechanical cleaning, (4) by dustless treatment. By a combination of any or all of these methods, coal can be prepared to standard specifications. It is easily possible to have good cleaning and still get a poor final product because of faulty screening or mixing,

Jan 1, 1943

By Charles T. Holland

IN connection with the problems of bumps in coal mines, much has been written concerning the manner in which roof action and methods of mining enter [ ] into the pressure effects observed but little has been written upon the relationship between the physical properties of coal and associated rocks and the cause of bumps. The question of the strength of bituminous coal, of its elasticity, and the energy it can absorb and store has been neglected to a considerable extent in connection with this problem. STRENGTH OF COAL It is generally agreed that one of the necessary conditions for bumps is a strong [ ] coal.1 Therefore, since the strength of coal is an important factor, a study of this property should be made. Several investigators have conducted laboratory experiments upon the strength of coal, using small cubical or rectangular test pieces. An attempt will not be made to go into all of these investigations, but they are briefly summarized in Table I. Experiments of the U. S. Bureau of Mines8 and of Lawall and Holland (pp. 27 and 34 of ref. 9), however, indicate that regardless of whether the coal is a soft and weak semibituminous (Pocahontas No. 3) or a hard and strong bituminous (Stockton) coal, the maximum ultimate unit stress developed in laboratory tests is higher in small cubes than in larger cubes of the same coal.

Jan 1, 1942

By D. E. Swets, R. C. Frank

It is well known that hydrogen is introduced into iron or steel as a result of many chemical processes (acid pickling, electrolytic cleaning, plating, etc.). One of the reactions that has been of recent interest1 is the reaction between an iron surface and water vapor. It was shown a few years ago2-4 that hydrogen can be introduced into steel at an accelerated rate during abrasion as a result of this reaction. Grun-berg and Scott have also observed that water in mineral oil lubricants increases pitting failure in ball bearings5 and they have suggested that hydrogen from the water is the primary cause of this effect.' In this laboratory, the question was raised as to whether or not hydrogen is also introduced into the metal surface of a bearing as a result of the decomposition of the hydrocarbon lubricant itself, and an experiment was performed to try to find a satisfactory answer. All steel parts contain some residual hydrogen. Therefore, it appeared that the best way to carry out this experiment without the need for highly accurate quantitative analyses was to use deuterium as a tracer. The natural abundance of deuterium in H2 is only 0.015 pct. The tracer was obtained in the form of deuteroparaffin (CD,(CDJ, CD,) and 0.25 g were dissolved in 20 cc of mineral oil to form the lubricant to be used in the tests. The bearings used were New Departure Type QOLOO ball bearings with a ball diam of 0.187 in. Prior to adding the mineral oil-deuteroparaffin lubricant, the bearings were cleaned in warm trichloroethylene to remove the packing grease. After packing with the new deuterated lubricant, the bearings were operated in a bearing fatigue test machine under a radial load of 190 lb and a thrust load of 190 lb at a speed of 3800 rpm. The expected life under these conditions is about 500 hr. Two tests were made; one for a period of 27 hr and the other for a period of 102 hr. The bearings achieved a temperature of 120o F during the tests. When the tests were stopped the balls were mechanically removed from the bearings and were immediately placed in liquid nitrogen to reduce degassing until the analysis for deuterium could be made. Before analyzing, the balls were warmed to room temperature and scrubbed with several degreasing agents to remove all traces of the deuteroparaffin mixture. This cleaning procedure was shown to be satisfactory by running a control test in which one ball bearing was subjected to all parts of the test except running in the fatigue machine. The hydrogen and deuterium were removed from the balls using a hot extraction apparatus attached to a mass spectrometer. Four balls from each bearing were analyzed. Each one was analyzed separately by removing it from a cold storage volume of the hot extraction apparatus and transferring it to the oven tube with a magnet. As the gases were evolved they were analyzed with the mass spectrometer. Since the hydrogen and deuterium pass through steel in the atomic form and since there are many more hydrogen atoms than deuterium atoms in the sample, the probability of forming an HD molecule is greater than forming a D2 molecule. For this reason the evolution of HD and H was followed as each ball was placed in the oven. The results showed that as each ball from the test bearing was dropped into the oven, the mass spectrometer recording of the HD evolution increased by about ten divisions. When balls from the control test bearing were dropped into the oven, the increase was about one division or less. The hydrocarbon background in the mass spectrometer was also monitored to see if hydrocarbons or deuterocarbons were given off when the balls were dropped into the oven, but no change in the hydrocarbon peaks was observed. Since the balls contained a fair amount of residual hydrogen, isotope ratio measurements were made on the gas obtained from each ball. The D/H value found for those balls which had been operated in the fatigue testing machine was consistently about 0.3

Jan 1, 1962

By J. C. Bokros

At temperatures above 950°F, zirconium which has been strained a critical amount will experience critical recrystalli-zation. The large grain size thus formed can result in a reduction in the fatigue life by a factor of 2 to a factor of 9 at both high and low temperatures. The critical strains for zirconium vary from 15 pct at 900°F to about 2 pct at 1125°F, while those for zircaloy III vary from 15 pct at 1050°F to 5 pct at 1200°F. Zircaloy II ,experiences no critical recrystallization up to 1200°F. ZIRCONIUM has become increasingly important for nuclear applications and is being employed in reactors at temperatures where recrystallization can occur. Recent work' on the fatigue properties of zirconium has shown that coarse-grained structures developed in zirconium during recrystallization have much lower fatigue lives than fine-grained material. The development of these large grain sizes under such conditions is well known to be the result of critical recrystallization.2-4 Briefly, critical recrystallization occurs when a metal is strained a critical amount and annealed in the recrystallization range. The critical strain is defined as that minimum strain necessary to promote nucleation in the time unit and temperature considered. The maximum grain size occurs at the critical strain, since at this strain the fewest stable nuclei per unit volume grow into new grains. Recrystallization is not evident below this; strain since the nucleation rate is vanishingly lolw, and metal strained more than the critical amount has a higher nucleation rate per unit volume which results in a finer grained structure. This paper describes the critical recrystallization observed in reactor-grade zirconium, zircaloy 11, and zircaloy I11 as a function of annealing temperature and temperature of strain. EXPERIMENTAL The zirconium used was hafnium-free, double arc-melted sponge obtained from the Bureau of Mines. The ingots were forged and hot reduced to 0.08 to 0.10-in. sheet and subsequently cold reduced to 0.035-in. sheet with intermediate and final anneals at 1200 OF for 15 min. The zircaloy II and zircaloy III used were 0.035-in. sheets in the annealed condition. Compositions of these materials as tested are given in Table I. To determine the critical strain at a given temperature, tensile specimens having a0.065-in. taper in a 2-in. gage length were machined from the sheets parallel to the rolling direction. The specimens were polished, etched, and examined metallographically to ensure that all of them were strain-free, initially. Tukon indentations were made every half millimeter along the gage length of each specimen. These served as fiducial marks enabling the plastic strain to be measured with a microscope and micrometer stage. The specimens were pulled to failure at a rate of 0.002 in. per min in an Instron tensile-testing machine. Three temperatures were used for straining: room temperature, 500 ºF, and 900 ºF. The 500º and 900 ºF tests were run in an argon atmosphere. Since the rate of work hardening changes with temperature, a different critical strain was obtained for each temperature of strain. Specimens, prepared in the manner described, were annealed in vacuunl at various temperatures ranging from 900" to 1200 F for up to 1000 hr, after which they were examined metallographically. The critical strain and the recrystallized grain size as a function of strain were determined for each specimen. Results for the same temperature and time indicated that the critical strain measured was reproducible to within 5 pct of each other. RESULTS AND DISCUSSION Since increasing the time of anneal increases the probability of the nucleation of a new grain, the critical strain decreases with time at a decreasing

Jan 1, 1961

By F. X. Tartaron

This article is a continuation of a previous paper by the writer in which Kick's Law was stated to be a part of comminution theory. ln the present paper, a broadening of ideas is attempted in order to state a general theory. The word "general" is employed because the new theory includes all previous laws and generalizations which are considered to be essentially correct. These ideas are combined into a coherent whole and the general theory can be expressed by the equation In the author's previous paper on comminution, ' the equations developed were based on Charles' equation of exponents a-n +1 = 0. 2 This paper is divided into two parts, designated as First Approach and Second Approach. In the First Approach, the equations of the previous paper are utilized, with Charles' equation of exponents being necessary. In the Second Approach, a separate and independent method is used to derive the same conclusions as in the First Approach, but without the use of Charles' equation of exponents. Holmes accepts the theoretical foundation of Kick's Law as sound but denies that the law as such operates in comminution. His idea is that Kick's Law requires homogenous matter whereas the presence of cracks, flaws and cleavage planes, which predominate in the coarser particles, makes matter unhomogene-ous. This explains why there is no experimental evidence to support Kick's Law. However, since the basis of the law is theoretically sound, all experimental evidence must be viewed as emanating from it. This requires modification of current comminution equations to fit this concept. Holmes makes the modification by changing the constant exponent n in the general energy equation used by Charles (E = - JCdx/xn) to a variable exponent r. The writer asserts that Kick's Law operates in comminution without modification but it does not

Jan 1, 1963

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p'robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI'U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts' wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.' This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d'~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU'~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By E. T. Turkdogan

The activities of SiO2, FeO, and Fe2O3 are calculated from previous experimental data on the activity of oxygen in Fe-Si-O melts at 1550°C. Using the oxide-activity data, the free energy of formation of fayalite from its oxides is evaluated for 1550°C. A number of investigators1-4 contributed to the study of the state of oxidation of iron in SiO,-FeO-Fe,O3 melts and the phase equilibria in the system Fe-Si-O. In a more detailed study, Schuhmann and Ensio5 and Michal and Schuhmann% easured the state of equilibrium in the SiO,-FeO-Fe,O3 melts saturated with y-iron or silica or both under low-oxygen potentials and within the temperature range 1250" to 1350°C. Similar measurements were also made by Turkdogan and Bills7,' over wide ranges of composition and oxygen potentials at 1550"C. Using the experimental data on the oxygen activities in the ternary system, Schuhmann' calculated the activities of silica and ferrous oxide in Si0,-FeO-Fe2O3 melts for 1350°C. Adequate knowledge on the activities of the constituent oxides of melts is essential in the study of reaction-equilibria and reaction-kinetics in oxide-melts. With this in view, the activities of oxides in SiO2-FeO-Fe2O3 melts at 1550°C are computed using the experimental data of Turkdogan and Bills7'8 on the oxygen activities in these melts.

Jan 1, 1962

By S. R. Seagle, R. Schuhmann, N. A. Parlee

Rates of CO evolution and CO absorption were measured for liquid-iron alloys containing from 0.15 to 4.4 pet C, using a modified Sieverts apparatus. The alloys were held in alumina crucibles, so that both crucible-metal and gas-metal reactions occurred simultaneously. The data are interpreted on the hypothesis that the C-O reaction rate is controlled by oxygen diffusion across the boundary layers at the gas-metal and crucible-metal surfaces. CARBON-monoxide evolution from liquid Fe-C-0 alloys is a key reaction in steelmaking processes, both in the steelmaking furnace and in the ingot mold. Also, this reaction probably is an essential step in the desulfurization of iron under blast-furnace conditions, for which carbon is the principal reducing agent or deoxidizer present in the iron. The thermodynamic properties of the solutions of C and 0 in Fe and the equilibria of these solutions with gaseous CO and CO, have been investigated in some detail and are reasonably well understood. However, while these equilibrium data have accumulated in the laboratory, other data have accumulated to show that equilibrium conditions are often not achieved under plant operating conditions. Thus, an understanding of the rate and mechanism of the carbon-oxygen reaction not only has theoretical interest, but ultimately may assume considerable practical importance. Reaction Mechanisms and Rate Equations The over-all reaction under consideration is C (in liquid Fe) + 0 (in liquid Fe) + CO (gas) [I] Although this appears to be a straightforward heterogeneous reaction, involving just two phases (liquid metal and gas), a wide variety of reaction mechanisms has been proposed. Different authors have expressed divergent views as to the nature of the rate-controlling steps. Accordingly, a brief discussion of the possible reaction steps will be given. 1) Homogeneous Reaction Within Liquid Iron— Feild' and Jette2 have applied chemical reaction-rate theory as if the C-0 reaction were a homogeneous, second-order reaction occurring within the liquid-metal phase. This mechanism necessarily produces CO "molecules" dissolved in liquid iron. In order to yield CO gas, the dissolved CO must nucleate CO gas bubbles, and the dissolved CO also must be transported to the bubble surface where it enters the gas phase. However, this mechanism is inconsistent with present concepts of the structure of liquid-metal solutions. 2) Reaction at Gas-Metal Interface—At the surface of contact between gas and metal, a second-order reaction between dissolved C and 0 may occur to produce a CO molecule which enters the gas phase. This reaction presumably involves an "activated complex" structure in the interface. Some such surface mechanism appears essential because the carbon and oxygen do not occur in the same species in the two phases and therefore must react in some way at the surface. At liquid-iron temperatures, calculations based on reaction-rate theory indicate that the surface reaction must proceed extremely rapidly and thus cannot be a rate-determining step in the C-O reaction under ordinary conditions.3 ccordingly when the over-all reaction is measurably slow, the surface reaction may be considered at equilibrium; that is Cc* Co* = m'Pco [2] in which Co* and Co* are the concentrations of carbon and oxygen (weight per unit volume of metal), respectively, in the liquid-metal phase at the interface, Poo* is partial pressure of CO in the gas phase at the surface (atmospheres), and m' is the mass-action constant for Reaction [I]. Since activities of C and 0 are not strictly proportional to concentrations, m' is not a true thermodynamic equilibrium constant but varies with carbon content.' 3) Mass Transport—If the reaction is to proceed at the gas-metal surface, as described above, dissolved carbon and oxygen in the liquid iron must come to the surface and gaseous carbon monoxide must move away from the surface. Details of the mass-transport mechanisms depend on the kind of system under consideration. For a stirred metal bath in contact with a CO gas phase, the transport of C and 0 to the surface can be described by 1 Do Mols CO evolved per sec = — 1/16— Do/do Agm (CO-Co*) = 1/12 Do/do Agm *(Co-Co*) [3] In this equation, Do and D, are the diffusion constants for oxygen and carbon in liquid iron, 6, and 6,. are the boundary-layer thicknesses, A,,,, is the

Jan 1, 1959