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By H. T. Byck

The plastering properties of six representative California drilling muds were studied over a temperature range of 70 to 175 F. at several mud weights, using a high-pressure circulating filter press with full size consolidated cores. In all tests, with untreated as well as with chemically treated muds, the filtration rates at elevated temperature were higher than at low temperatures and in nearly every case this increased filtration rate was notably larger than could be attributed alone to the decreased viscosity of water—the flowing medium—at elevated temperatures. It is concluded that no existing method will permit even an approximate determination of the filtration rate at high temperature from data at room temperature. It is necessary to measure filtration at the temperature actually anticipated in the well, or to make a sufficient number of tests at various lower temperatures so that a small extrapolation of these data to the anticipated well temperature may be applied. Such tests should be carried out on the mud as actually used in the well. The viscosity of each of the muds was determined over the same temperature range. While no relationship was observed between mud viscosity and plastering properties, it was found that chemical treatment of the muds for viscosity reduction shifted the temperature of minimum viscosity to appreciably higher values than for untreated muds. Importance of Plastering Properties A survey of the literature on rotary drilling muds clearly shows the growing realization of the importance of plastering properties,'-5 not only from the point of view of the successful completion of the mechanical operation of drilling the well but also from the point of view of minimum impairment of the natural flow possibilities of a given well. Poor plastering properties with attendant high filtration rate (large water loss to the formation) and thick mud sheath, lead to stuck drill

Jan 1, 1940

By Arthur J. Boynton

In the preparation of this paper the writer has been influenced by the fact that descriptions of various means of cleaning blast-furnace gas have been published and that further descriptive treatment of the subject will probably be less interesting than a statement of conclusions with regard to preferable methods which have been reached by him as a result of experience and observation in this country and also as a result of somewhat detailed investigation of the subject made toward the end of the year 1927 on the Continent of Europe and particularly in Germany. Owing to various circumstances, including a cost of fuel that is extremely high in relation to the wages of labor, the German iron and steel industry has accumulated experience in gas washing which is as yet in part lacking in the United States of America. The paper begins with a statement regarding the economics of the use of blast-furnace gas, then considers the principles and practices employed in its purification. Uses of Blast-furnace Gas For many reasons having to do with the utilization of coke-oven and blast-furnace gases in steel manufacture and with the use of hot metal, the blast furnace is now usually a part of a steel-producing unit, which also includes coke plant and rolling mill. Therefore both blast-furnace and coke-oven gas are usually applicable to any of the iron and steel-making processes, including the generation of power, and their allocation in any given works should be considered as a single problem. The uses to which blast-furnace gas, either alone or mixed with coke-oven gas may be put, include the following: Regenerative Heating of Ail. for the Blast Furnace.—This is the oldest and metallurgically the rnost important of all uses. It is universally performed with unmixed blast-furnace gas and under proper conditions should require not over 23.5 per cent. of the total gas generated for a blast temperature of 1350" F. For Steam-raising Purposes.—This is almost universally done with unmixed blast-furnace gas. From the standpoint of quantity used, it is at the present time the most important application in American steelworks practice.

By Arthur Boynton

IN THE preparation of this paper the writer has been influenced by the fact that descriptions of various means of cleaning blast-furnace gas have been published and that further descriptive treatment of the subject will probably be less interesting than a statement of conclusions with regard to preferable methods which have been reached by him as a result, of experience and observation in this country and also as a result of somewhat detailed investigation of the subject made toward the end of the year 1927 on the Continent of Europe and particularly in. Germany. Owing to various circumstances, including a cost of fuel that is extremely high in relation to the wages of labor, the German iron and steel industry has accumulated experience in gas washing which is as yet in part lacking in the United States of America. The paper begins with a statement regarding the economics of the use of blast-furnace gas, then considers the principle's and practices employed in its purification. USES OF BLAST-FURNACE GAS For many reasons having to do with the utilization of coke-oven and blast-furnace gases in steel manufacture and with the use of hot metal, the blast furnace is now usually a part of a steel-producing unit, which also includes coke plant and rolling mill. Therefore both blast-furnace and coke-oven gas are usually applicable to any of the iron and steel-making processes, including the generation of power, and their allocation in any given works should be considered as a single problem. The uses to which blast-furnace gas, either alone or mixed with coke-oven gas may be put, include the following: Regenerative Heating of Air for the Blast Furnace.-This is the oldest and metallurgically the most important of all uses. It is universally performed with unmixed blast-furnace gas and under proper conditions should require not over 23.5 per cent. of the total gas generated for a blast temperature of 1350° F. For Steam-raising Purposes.-This is almost universally done with unmixed blast-furnace gas. From the standpoint of quantity used, it is at the present time the most important application in American steel-works practice.

Jan 1, 1928

By M. Takeda, H. Majima

Pyrite has been subjected to xanthate adsorption experiments in order to determine the nature of adsorption. The identification of adsorbed species by means of IR spectroscopy, as well as UV, shows that the dixanthogen adsorption is undoubtedly predominant on pyrite surface. The rest potential measured in a xanthate solution coincides with the redox potential of the xanthate-dixanthogen couple. Considering all the factors together, the adsorption mechanism of dixanthogen on pyrite has been proposed as This mechanism is consistent with the "passive" character of pyrite. From the measurement of the redox potential of the xanthate-dixanthogen couple in the homologous series, a rule similar to that for surface tensions proposed by Traube is also applicable. The polarization experiments were conducted on pyrite in a solution containing xanthate. In the anodic polarization, xanthate is observed to oxidize to dix- anthogen, which depresses oxygen evolution on py rite at higher potential levels. In spite of the importance of the presence of pyrite in the flotation of sulfide minerals, not many studies have been made on the xanthate-pyrite system in the absence of an activator or a depressant. In an early study by Gaudin and Wilkinson,' it was pointed out that no ferric xanthate was formed on a pyrite surface, while in another study Gaudin and his collaborators2 proved the formation of a very small amount of ferric xanthate. Afterwards, Gaudin et al.3 studied the pyrite-xanthate system with a radiometric technique and found indications of the presence of adsorbed dixanthogen on pyrite surfaces. Mamiya4 studied the flotation behavior of the pyrite-xanthate system and also suggested the possibility of dixanthogen. Recently, Fuerstenau and his coworkers at The Colorado School of Mines5 studied the role of dixanthogen in the xanthate flotation of pyrite and discussed the problem in terms of such properties as oxidation potential, zeta potential, flotation recovery, pH of solution, etc. However, the mechanism of dixanthogen adsorption at the pyrite-water interface is not yet understood. This paper is concerned with an electrochemical in-vestigation through which the mechanism of dixanthogen adsorption on pyrite is interpreted. EXPERIMENTAL MATERIALS AND TECHNIQUES Pure potassium xanthates were synthesized by an

Jan 1, 1969

By James Norman, E. W. Gieseke

SPODUMENE is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content. it might be a desirable constituent of glass batches. The use of spodumene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components.1 The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manganese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li20 on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston, [t] the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2, 3 The methods described in the second publication3 did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted. STUDY OF METHOD OF FLOTATION SEPARATION Most of the work on concentration of spodumene was done with rock from near King's Mountain, North Carolina. Rock from two

Jan 1, 1940

By Alden B. Greninger, Alexander R. Troiano

THE crystallographic mechanism for the austenite-to-martensite transformation has been deduced from the results of the following new experimental determinations: (I) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite-and thus the relationship between the martensite lattice and the martensite plate, and (2) the measurement and analysis of the change in positions that a volume of austenite undergoes when it transforms into a crystal of martensite. For the latter study, a new tool was developed, the stereographic analysis of shear. Lattice relationship.-Thirty-five separate 50-gram melts of an alloy containing about 22 per cent nickel and 0.8 per cent carbon were prepared in a high-vacuum furnace. This alloy is all-austenite at room temperature; grain size was about I cm. Specimens of the alloy were cooled to about -70°C. to form a few martensite crystals, and suitable specimens were ground and polished on a surface parallel to a single martensite plate, exposing the martensite crystal for an area of I mm. or more. Four martensite cystals from four different ingots were prepared in this manner; the largest crystal of this group is illustrated in Fig. I. Back-reflection Lane patterns were obtained from martensite [ ] crystals (and the matrix austenite) both before and after tempering. The locations of the basal-plane pole of martensite was checked by means of oscillating crystal X-ray patterns. All four crystals studied yielded the same solution (±0.5°), and these relationships are expressed in gnomonic projection in Fig. 3.* The narrow dark-etching bands often visible in martensite "needles" were found to be parallel to {112} and thus are undoubtedly twin bands in the martensite crystal.

Jan 1, 1941

By C. D. Hunter, J. B. Browning

During the year 1934, Kentucky oil and gas operators have partly overcome their past depression fears and in the oil industry, with possibly more abandonments of old oil producers than the completion of new oil wells, produced 4,814,904 bbl. of oil in 1934 against 4,501,511 bbl. in 1933. In the gas industry of eastern Kentucky, 115 gas wells were completed during 1934. This production is delivered through two 20-in., one 16-in., one 12-in., one 10-in., and two 8-in. pipe lines to supply both domestic and industrial markets in Cincinnati, Ohio; Louisville, Lexington, Frankfort, Winchester, Ashland, Covington and other Kentucky towns; Washington, D.C., and other eastern cities. The largest percentage of these gas wells and production are from the Devonian black shale area of Floyd, Pike, Knott, Martin and Magoffin counties, Kentucky. In this area the largest percentage of 1889 wells, developing 421,-215 acres, has been completed in the past 10 years, of which 55.3 per cent produce from the 400 to 550 ft. of Carbonaceous Devonian black shales. The successful results obtained from these Devonian shales are due to the physical effects of the 5000 to 6000 lb. of gelatinated nitroglycerin with which the entire 400 to 550 ft. of shale is shot. A very small number of the shale wells are natural producers and do not require shooting. Other than the Devonian shale gas production, the remaining 44.5 per cent of the gas in this field is encountered throughout the entire strati-graphic section above this horizon; namely, salt sands of Pennsylvanian age and Maxon, Big Lime and Weir of Mississippian Age. A very small percentage is encountered in the Corniferous Devonian lime and the Silurian Big 6 below the black shales. In western Kentucky, in the counties of Henderson, Webster, Hopkins, McLean, Christian, Muhlenburg, Ohio, Daviess, Hancock, Brecken-ridge, Hart, Barren and Warren, many gas wells have been completed, but, because of insufficient market, activity has been somewhat desultory. The area is served by the pipe lilies of the Kentucky Natural Gas Corporation, with headquarters at Owensboro. Their market is increasing and the gas is delivered to Owensboro, Henderson, Madisonville, and many

Jan 1, 1935

THERE is probably no phase of basic open-hearth steelmaking that is more of an art and less of a science than mold and pouring practice. It varies widely from plant to plant; consequently it is obviously impossible to set down in detail in this chapter the many ramifications of practice that are now used. The discussion that follows therefore attempts only to give an outline of the more common methods, with examples sufficient to indicate some of the variations in procedure, and to emphasize a few of the many underlying problems that face the open-hearth operator at the pouring platform. MOLD DESIGN Ingot molds are hollow castings of considerable wall thickness. Despite this, non-uniformity in wall thickness should be strictly avoided to prevent the setting up of unnecessary stresses. Molds are cast in various forms, sizes, and shapes depending on the type of steel, and on whether the ingot is to be withdrawn from the mold or the mold from the ingot. The selection of ingot-mold material, which is usually cupola or blast-furnace iron containing approximately 3.5 per cent carbon, 1 per cent silicon, 0.9 per cent manganese, 0.2 per cent phosphorus, and 0.07 per cent sulphur, is governed by numerous considerations that affect mold life. (1) Factors in addition to wall thickness that should be given primary consideration at the foundry are casting skin, shrinkage stresses, and casting temperature. Factors in Mold Design. In use, mold thickness is of greatest importance, for it must be heavy enough to freeze the molten metal rising in the mold and to reduce the temperature of the steel below that of the melting point of cast iron to prevent the inner surface of the mold from melting, which would result in the welding of the ingot to the mold. The skin of an ingot, which solidities immediately upon contact with the relatively cold walls of the mold, must soon become thick enough to contract on the fluid mass and pull away slightly from the sides of the mold. The separation of the ingot from the mold depends entirely on the heat taken up by the mold from the steel.

Jan 1, 1944

By Franz R. Dykstra, R. F. Tatnall

A ferroalloy is defined as: "An alloy of iron with some element other than carbon used as a vehicle for introducing such an element into the manufacture of steel. The element may alloy with the steel by solution or, as the carbide, -neutralize the harmful impurities, by combining with them and separating from the steel as flux or slag before solidification."a The most commonly used ferroalloys are: ferromanganese, ferrochrome, ferrosilicon, ferrovanadium, ferromolybdenum, ferronickel, ferrotungsten, ferrocolumbium, and ferrophosphorus. Concern here is with the sources and markets of the major metallic alloying elements. The discussion is further restricted to those - ferroalloy ores, the principal use of which is in the production of steel. Phosphorus, silicon, and tungsten, for example, are ferroalloys of some economic significance, but other uses dwarf their alloying applications. Thus, this discussion will deal with the ores of managanese, chromium, nickel, molybdenum, vanadium, and columbium. As shown in Table 14.1B.1 ferroalloys serve to- facilitate processing and impart to the finished steel such characteristics as tensile strength, ductility, low-temperature impact, hardenability, high-temperature strength, corrosion resistance, toughness, and abrasion resistance. In the steel-making process, ferroalloys may be added in the charge, in the molten bath near the end of the finishing period, in the ladle, or in the molds. Timing of the addition depends on the effect of the addition on the temperature of the molten metal, the formation and elimination of reaction products, and the protection of subsequent additions from oxidation. MANGANESE General Approximately 95% of the manganese ore sold is consumed by the steel industry, either as ferromanganese or as manganese metal. Manganese is the universal alloy, without which good steel cannot be made. It serves as a scavenger, removing phosphorus, sulfur and, to a degree, oxygen from the melt. As an alloying material it makes steel hard, tough, and resistant to wear. Approximately 6 kg of manganese is required for every ton of common steel produced by United States steelmaking practice. The remaining 5 % of the manganese ore consumed consists of special or so-called "chemical" ores, including high-grade pyrolusite ores, electrochemically reactive "battery ores," and a number of special varieties, as well as those otherwise regarded as "metallurgical ores."

Jan 1, 1976

By A. Poll, J. E. Stantan, L. J. Jolley

THE basic problem in the generation of water gas from carbonaceous fuels and steam is the supply of the heat of reaction, and in general the source of this heat is the combustion of a further quantity of carbon with oxygen. Existing and proposed processes for complete gasification differ in the methods employed for transferring this heat to the fuel, and involve one or other of the following alternatives: 1. Use of a steam-oxygen mixture as the gasifying medium, so that the combustion and gasification reactions are combined. 2. Alternate passage of air and steam through a fixed bed, as in conventional water-gas production. 3. Cyclic passage of fluidized fuel through combustion and gasification zones. 4. Intense preheating of steam and of a portion of the gas made, and recirculation of this mixture through the fuel bed. 5. Supply of heat to the fuel bed through an externally heated wall. Except for the conventional water-gas process using large coke or low- volatile coal, only processes in the first group, operating with steam and oxygen, have proved practicable with fuels other than brown coals and lignites. A possible exception, which has not so far reached a commercial scale, is the moving-burden process developed by Imperial Chemical Indus- tries, Ltd. The cost of industrial oxygen is so high that its use can probably be justified only if it is attended by substantial savings in other directions; for instance, the use of cheap fuel. In the United Kingdom, no very cheap solid fuels are available, and it is unlikely that an oxygen-gasification process could compete economically with conventional production of blue water gas from coke. Hence particular interest attaches to all possibilities of making water gas without using oxygen, if any possible saving in fuel or other costs is involved. The cheapest and most abundant coals in the United Kingdom are the low-rank noncaking bituminous coals in small and ungraded sizes, typically those from the East Midlands coal field, and-fines of high ash content produced in coal-cleaning operations. A process capable of gasifying

Jan 1, 1953

By Walter S. Weeks

THE subject of the flow of air through a mine under the influence of natural ventilation has proved an elusive one. To my knowledge only cut and try algebraic solutions have been used where multiple paths are involved. The object of this paper is to present a method for the graphical determination of the flow induced by the natural ventilation pressure (N.V.P.) alone or in combination with a fan. The N.V.P., measured in pounds per square foot, induced by two columns of air between two horizontal planes at different elevations, is equal to the difference in weight of the two columns, assuming each to have a cross-sectional area of 1 sq. ft. Pressure in pounds per square foot is converted into inches of water by dividing by 5.19. Methods of calculating the N.V.P. have been discussed in the literature. In this paper, for simplification of exposition, the change in pressure due to the weight of superimposed air will be assumed directly proportional to the length of the column. The actual methods of calculating the N.V.P. do not affect the solutions to be presented. It must be realized that the precision to be obtained from the small- scale, inked diagrams presented is not as great as would be obtained from large-scale, penciled curves that would be used in practice. The accuracy of the curves does not warrant reading "volumes" closer than the nearest thousand cubic feet per minute. CASE I. DUCTS IN SERIES The simplest type of problem is to determine the flow when two shafts are connected by a crosscut, as shown in Fig. 1. In this example, the resistance of the shafts is to be taken as 0.0001 in. of water for a flow of 1000 cu. ft. per minute for a length of 1000 ft. The resistance of a crosscut is to be taken as 0.0005 in. of water for a flow of 1000 cu. ft. per minute. The small pressures necessary to cause changes in velocity will not be considered, because the accuracy of other obtainable data does not warrant their consideration.

Jan 1, 1938

By J. O. Whiteley, C. Dietz

It is difficult to give a refining outline that may be followed for any and all combinations of the platinum metals; different combinations require different methods of attack. This paper does not pretend to go into all of the reactions of the metals of the platinum group, but will outline the commercial refining of platinum scrap. Typical Platinum Scrap As a concrete case, let us take 100 oz. of miscellaneous scrap, made up of jewelry scrap, dental scrap and laboratory ware. This lot will contain some platinum, palladium, iridium, ruthenium, rhodium, gold, silver and copper. The first problem is to get all of the metals in solution. If the scrap is principally platinum, palladium and gold, a treatment with aqua regia is the course to pursue; but if the scrap contains alloys high in iridium or ruthenium, aqua regia will act too slowly. In the case in hand, we are going to presume that we have scrap high in iridium and ruthenium, and proceed accordingly. Obtaining Residue A Place the scrap, together with six times its weight of granulated test lead, in a solid carbon crucible. This crucible may be placed inside a clay graphite crucible packed with charcoal, to prevent the excessive oxidation of the carbon crucible by the furnace blast. Place a tight cover on the carbon crucible; heat gradually to a good red heat and allow it to soak in the heat for 4 or 5 hr. After the leaded mass is cool, dissolve in dilute nitric acid (1-6) on a steam plate or sand bath. This dissolves practically all of the lead and most of the palladium, silver and copper, together with seme of the platinum and rhodium, and leaves the iridium, ruthenium, gold, and most of the rhodium and platinum as a finely divided residue. Siphon off the clear solution and treat the residue with another portion of dilute nitric acid to insure the solution of the lead and copper. The second nitric acid solution is added to the first, and the residue is filtered on suction and washed thoroughly with hot

Jan 1, 1928

By George C. Stone

The stack gases from regenerative furnaces lare very seldom utilized for the production of steam. If the temperature of the gases is not higher than 300" C. (572" F.) there is no economy in their use for this purpose, as the amount of available heat is very small and the temperature is so little above that of the steam that the interchange is too slow. With higher temperatures of the waste gases, however, good results can be obtained. At the plant of the New Jersey Zinc Co. (of Pa.) at Palmerton there are a number of return tubular boilers, each 6 ft. in diameter and 20 ft. long, with 96 3.5-in. tubes, which are heated by the waste gases from the spelter furnaces. These furnaces have continuous regenerators heating the air only and the stack gases reach the boilers at a temperature of about 450". The gas producers for one of these furnaces require 14 tons of anthracite (a mixture of Nos. 2 and 3 buckwheat), and the waste heat from the furnace gives a little more than 42 h.p. in steam. The boilers are not well adapted for the purpose, as they are much too large for the amount of heat going to them and the area of the tubes is not sufficient to take the gas from two furnaces without causing an objectionable amount of back pressure. The plant was built without any idea of using waste-heat boilers, and it was impossible to place the latter as close to the furnaces as they should be. Furnace and boiler are connected by an underground brick flue in which the temperature of the gas drops about 100°, losing 40 per cent. of its available heat. If the boilers were close to the furnaces the horse power of each would be 70 instead of 42. Even under these unfavorable conditions the boilers have been very advantageous, as one boiler easily supplies the steam necessary for two batteries of producers. With such low gas temperatures the heating surface of the boilers is, of course, not as efficient and the flue areas need to be considerably larger than for coal firing.

Jan 1, 1914

By Eugene Guccione

Evidence that the United States is gradually converting to the metric system of measurement can be perceived today even by housewives in a supermarket. The question is no longer whether but when the country will have completed the conversion. To the extent that any bickering about metrication still exists, the debate now centers on such issues as finding agreement on details of implementation, and whether federal legislation should speed up the metric-conversion process or allow it to proceed along its present evolutionary and voluntary course. Apparently, the voluntary or "make-haste-slowly" approach is gaining widespread support. According to The Research Institute of America, Inc., if and when federal legislation is enacted it will likely include the following national ground rules: (1) A National Metric Conversion Board will develop and submit to the President and Congress a comprehensive plan to achieve a coordinated, minimum-cost changeover. (2) The change- over will be completed 8 to 10 years after the board's plan goes into effect, and by that time the US will be predominantly, though not exclusively, metric. (3) Costs will "lie where they fall"; subsidies, special tax concessions, and antitrust exemptions will not be authorized by the legislation. (4) The changeover will be voluntary because of the recognition that while some firms can "go metric" in a matter of weeks, others may require 15 years or more, and a few might never convert. (5) In determining whether or not to convert, on an individual company basis, adherence will be to the "rule of reason-that is, ". . . do not convert unless the engineering, economic, or other benefits outweigh any metric-related disadvantages. No one is talking about rip- ping up our railroad tracks or rewiring our homes just to conform to the practice of metric nations in Europe." (6) Government is to be part of the solution, not part of the problem; in effect, says The Research Institute of America, the leverage of federal procurement will not be exerted to force-feed the metric changeover but will be coordinated with the sector-by-sector conversion of the economy.*

Jan 12, 1975

G. B. WATERHOUSE,* Buffalo, N. -Y. (written discussion?).-One of the most essential features of rail manufacture is the production of rails that will give good service and be free from failures. To this end rails are made to careful specifications and their manufacture is controlled by rigid inspection on the part of both the producing mill and the railroad or its representative, such as the Hunt special inspection referred to in the paper. Captain Hunt refers to the crescent-shape base failures and describes them as ruptures in the rail flanges extending from the outside inward toward the web. This is hardly correct and may be misleading. It has been shown, over and over again, that the base breaks originating in seams invariably start at the center of the rail base; and run longitudi-nally in varying lengths from 3 to 12 in. and sometimes longer. Most of them are from 5 to 8 in. long and then curve outward to the edge of the flange. The split at the center of the base may exist for an indefinite time and not be discovered until the break shows on top of the flange or the piece of flange breaks off. The. stresses that cause the break are explained in two ways: (1) by the eccentric bearing of the rail base, that is taking contact at one side or edge and bringing excessive strain at the center of the base which starts fracture in any seam that may he present at that point; (2) the split may be due to cross strain in the base where this member is thrown into. compression, as happens where a pair of trucks are on opposite sides of the cross tie or rail-base hearing, and the head is put in tension. A careful study of "split base breaks" shows that fully 95 per cent. occur on the tie bearing, which is further evidence that the above de-scribed causes for the initial break are probably correct. These split base breaks are almost invariably progressive, but always start at the center of the rail-base running longitudinally.

Jan 12, 1919

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By D. Weinstein

The high temperature mechanical properties of stainless steels after fast neutron irradiation are discussed in the light of effects caused by lattice dattmage and effects caused by helium generated from n,a transmutations. Embrittlement at high temperatures is due to helium accumulation at grain boundaries and to cavity formation and proPagation along grain boundaries. Following from the embrittlement mechanism, it is suggested that when deformation occurs by mechanisms associated with super plasticity, helium ac-curnulation at boundaries should be attenuated and cavities, if formed, should be nonpropagating. As the mean free Path between interphase boundaries of a two-phase Fe-Cr-Ni alloy was decreased, the degree of superplastic deforrnation at 870°C increased, as vneaszired by total elongation and by the expottent m = a log 'a/a log 'i. This alloy and type 304 stainless steel were cyclotron irradiated in an a-particle beam to a helium concentration of -1 x 10 atom He per atom. The stainless steel specimen was embrittled, but the ductility of irradiated two-phase Fe-Cr-Ni alloys correlated with the values of. m during 'defor-malion. The .finest grained, helium-injected specimens that deforrned with highest m values exhibited the largest elongations to ,fracture. These results could be correlated with metallographic observations of cavity behavior: the propensity for intergranular propagation was lessened as the m value increased. It is concluded that superplastic deformation is ef-fectizle in attenuating helium embrittlement at elevated temperatures. One of the principal problems associated with development of fast breeder reactors is application of alloys such that suitable fuel cladding results. Stainless steels and other Fe-Cr-Ni alloys, because of highly acceptable nuclear characteristics, represent the primary materials for this component, and an exhaustive research and development effort is being conducted. The main deficiency of these materials has been a severe loss of ductility at high temperatures after fast neutron irradiation. An extensive body of mechanical property data and microstructural observations has provided an adequate phenomenological description of embrittlement; in conjunction with transmission electron microscopy studies, a reasonably acceptable embrittlement mechanism has been obtained. Following from this mechanism, it is suggested in the present work that ductility would be enhanced if deformation could occur by mechanisms associated with the phenomenon of superplasticity. Experiments to test this hypothesis have been conducted, and the results are presented and discussed in this paper. IRRADIATION EMBRITTLEMENT AT HIGH TEMPERATURE Austenitic stainless steels have been irradiated to accumulated fast neutron fluences of 1020 to 1022 nvt at temperatures between 60" and 600°C. Specimens that have been exposed to these conditions and subsequently tensile tested at temperatures between 600" and about 900°C exhibit approximately 5 pct total elongation to fracture.'-3 For unirradiated specimens receiving a nearly identical thermal exposure, total elongation at these test temperatures is about 45 pct. Examination of irradiated specimens has shown that fracture propagation is entirely intergranular. These phenomenological aspects of irradiation embrittle-ment at elevated temperatures are well known and are not generally disputed. Although the explanation of this phenomenon has been controversial, a mechanism for ernbrittlement has emerged that accounts reasonably well for the observed mechanical behavior. The controversy resulted primarily from an indeterminate role of neutron-in-duced lattice damage, if any, and a presumed, but experimentally unverified, contribution to embrittle-ment from helium generated by n,a transmutations. Recently, Holmes and coworkers4 have conducted experiments that separate these effects, and the results are instructive in formulation of the ernbrittlement mechanism. Holmes el al.4 irradiated type 304 stainless steel in EBR-I1 to a fluence of 1.4 x 1022 nvt (E > 0.18 mev); the irradiation temperature was 538" * 48°C or, in terms of absolute melting point, 0.49 * 0.03 T,. After irradiation, tensile tests were conducted at temperatures of 21" to 870.C, the specimens first being annealed for 30 min at each test temperature. In addition, thin sections of irradiated specimens were annealed for 1 hr at identical temperatures, electro and examined by transmission electron microscopy. Thus, for a given temperature, it was possible to correlate mechanical properties with the defect structure. At room temperature, the yield stress of irradiated specimens was a factor of 2.5 higher than unirradi-ated specimens exposed to an equivalent thermal history. Electron microscopic examination of the irradiated specimen revealed a high density of lattice damage in the form of Frank sessile dislocation loops and polyhedral voids. Holmes et al.4 concluded that the presence of this defect substructure caused the increase in yield stress and that after irradiation in a fast neutron flux at 0.49 Tm, substantial lattice dam-age persists. Annealing at progressively higher tem-

Jan 1, 1970

By Samuel L. Hoyt

This paper gives a brief description of an investigation made several years ago on the diffusion of zinc into copper. The material for that study was furnished in the form of thin copper strips coated with zinc. The result was required rather quickly and at not too great an expense, and especially information was desired as to the rate at which zinc would diffuse from the zinc coating into the copper and the temperature at which the operation should be carried out. A study of the requirements of this problem indicated that the solution might be secured by means of six determinations. This is the smallest number that will give the information desired and, at the same time, furnish checks on the accuracy of the determinations which justify an abbreviated experimental program. This does not count a preliminary test which was designed to give some idea of the correct temperature to use. The minimum number of temperatures that can be used is two. Knowing the rates of diffusion of zinc into copper at two properly chosen temperatures, it is possible to calculate the rate for any other temperature, and also to check the accuracy of the determination by means of the heat of diffusion, which is calculated from the effect of temperature on the rate of diffusion. The minimum number of determinations at any one temperature is three. The amount of diffusion which occurs at a fixed temperature is definitely related to the time of diffusion, so that by determining the amount of diffusion for three different time intervals, this relationship may be established and possibly a check on the accuracy may be secured. This accounts for the six determinations or experiments, and suggests the logical plan of the work. The check used here is not generally applicable to diffusion phenomena, but it seems to hold closely enough for the limited amount of diffusion in this investigation to justify its use. The samples used were 5 to 6 mils thick and about 1 in. square. They were placed between iron blocks and set in the hot zone of a nichrome furnace which had been brought to the desired temperature Time was taken from the moment the samples reached the furnace

Jan 1, 1929

By Samuel L. Hoyt

This paper gives a brief description of an investigation made several years ago on the diffusion of zinc into copper. The material for that study was furnished in the form of thin copper strips coated with zinc. The result was required rather quickly and at not too great an expense, and especially information was desired as to the rate at which zinc would diffuse from the zinc coating into the copper and the temperature at which the operation should be carried out. A study of the requirements of this problem indicated that the solution might be secured by means of six determinations. This is the smallest number that will give the information desired and, at the same time, furnish checks on the accuracy of the determinations which justify an abbreviated experimental program. This does not count a preliminary test which was designed to give some idea of the correct temperature to use. The minimum number of temperatures that can be used is two. Knowing the rates of diffusion of zinc into copper at two properly chosen temperatures, it is possible to calculate the rate for any other temperature, and also to check the accuracy of the determination by means of the heat of diffusion, which is calculated from the effect of temperature on the rate of diffusion. The minimum number of determinations at any one temperature is three. The amount of diffusion which occurs at a fixed temperature is definitely related to the time of diffusion, so that by determining the amount of diffusion for three different time intervals, this relationship may be established and possibly a check on the accuracy may be secured. This accounts for the six determinations or experiments, and suggests the logical plan of the work. The check used here is not generally applicable to diffusion phenomena, but it seems to hold closely enough for the limited amount of diffusion in this investigation to justify its use. The samples used were 5 to 6 mils thick and about 1 in. square. They were placed between iron blocks and set in the hot zone of a nichrome furnace which had been brought to the desired temperature Time was taken from the moment the samples reached the furnace

Jan 1, 1929

By George Stone

THE stack gases from regenerative furnaces are very seldom utilized for the production of steam. If the temperature of the gases is not higher than 300° C. (572° F.) there is no economy in their use for this purpose, as the amount of available heat is very small and the temperature is so little above that of the steam that the interchange is too slow. With higher temperatures of the waste gases, however, good results can be obtained. At the plant of the New Jersey Zinc Co. (of Pa.) at Palmerton there are a number of return tubular boilers, each 6 ft. in diameter and 20 ft. long, with 96 3.5-in. tubes, which are heated by the waste gases from the spelter furnaces. These furnaces have continuous regenerators heating the air only and the stack gases reach the boilers at a temperature of about 450°. The gas producers for one of these furnaces require 14 tons of anthracite (a mixture of Nos. 2 and 3 buckwheat), and the waste heat from the furnace gives a little more than 42 h.p. in steam. The boilers are not well adapted for the purpose, as they are much too large for the amount of heat going to them and the area of the tubes is not sufficient to take the gas from two furnaces without causing an objectionable amount of back pressure. The plant was built without any idea of using waste-heat boilers, and it was impossible to place the latter as close to the furnaces as they should be. Furnace and boiler are connected by an underground brick flue in which the temperature of the gas drops about 100°, losing 40 per cent. of its available heat. If the .boilers were close to the furnaces the horse power of each would be 70 instead of 42. Even under these unfavorable conditions the boilers have been very advantageous, as one boiler easily supplies the steam necessary for two batteries of producers. With such low gas temperatures the heating surface of the boilers is, of course, not as efficient and the flue areas need to be considerably larger than for coal firing.

Jan 10, 1913