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By G. B. Gould, F. M. Gibson

IN DECEMBER, 1934, the joint Committee on Fuel Values, of the American Institute of Minim and Metallurgical Engineers and the American Society of Mechanical Engineers, submitted a preliminary report, which briefly stated its conclusion that it was not possible to devise any formula for the valuation of coal, based upon the various physical and chemical properties, that would be generally applicable. That report also listed those chemical and physical properties of coal that are generally recognized to have some effect on its use in steam plants, and those physical characteristics of steam plants which affect, in one way or another the relative importance of the properties of coal used in them. Since then, the Committee has considered and discussed in greater detail the interrelationship of the properties of coal and plant characteristics. The conclusions of the Committee are summarized below, with certain recommendations regarding engineering procedure, which will promote the collection of more easily correlated observations with respect to this subject, and thus advance more rapidly the accumulation of data capable of general application.

Jan 1, 1936

By James W. Halley

' FINE-GRAINED " steels have been standard products for many years. This paper describes an investigation of the effects of some of the more common grain-growth; inhibitors used to produce these steels. The properties, response to heat-treatment, and the deoxidation practice necessary to produce "fine-grained" steels have been the subjects of numerous papers. It has been shown that a substantial quantity of' aluminum is necessary to produce this type of steel, and it has been indicated that titanium and zirconium produce a similar result. For some time there was a lively argument between those who felt that aluminum refined the grain and those who felt that aluminum oxide was the effective agent. This argument subsided with an apparent victory for those promoting aluminum oxide. Most of the work on grain size has divided steels into two broad classifications based upon McQuaid and Ehn's original carburizing test at 1700°F. or some similar test at this temperature. If the steel coarsened at this temperature, it was coarse grained, while if it did not it was fine grained. Quantitative data concerning how much a certain amount of aluminum raised the coarsening temperature and affected the properties, all other factors being constant, are very meager. Similar information regarding titanium and zirconium is practically nonexistent. The published information on aluminum yields some quantitative information. Epstein, Nead and Washburn' gave the first quantitative information on the amount of aluminum necessary to prevent grain growth at 1700°F. They showed that the addition of a pound to a pound and a half of aluminum per ton (0.05 to 0.075 per cent) would assure steel that would not .coarsen during a McQuaid-Ehn test at 1700°F. Herty, McBride and Hough2 reported that a steel containing 0.020 per cent acid-soluble aluminum coarsened between 1742° and 1832°F., while steels containing 0.016 per cent and 0.017 per cent acid-soluble aluminum coarsened between 1652~ and 1742°F. compared with similar aluminum-free steels that started to coarsen at 1580°F. Herty3 also showed a marked improvement in low-temperature notched impact resistance with increasing acid-soluble aluminum up to 0.030 per cent. McQuaid4 compared the coarsening of steels containing 0.011 to 0.204 per cent total aluminum and found a maximum coarsening temperature at 0.098 per cent aluminum. He had no samples between 0.015 and 0.098 per cent aluminum. Houdrement5 found a marked decrease in coarsening temperature with aluminum contents above 0.50 per cent. Kinzel, Crafts and Egan6 found that aluminum and zirconium improved thy low-temperature impact resistance of a low-alloy steel, while titanium was detrimental. Sims7 shows that sulphur increases the coarsening temperature and that the maximum coarsening temperature is between 0.04and 0.06 Per cent added aluminum. The

Jan 1, 1946

By Walter R. Hibbard, Harold Margolin

The effect of ten ternary additions on the aging of a Cu-Ag alloy was measured by X ray, microstructure and hardness. A supersaturated copper-rich transition structure was found. The effect of the ternary element was related to differences between transition and precipitate lattice parameters and analogies with solution and strain hardening. IN addition to the prerequisite of diminishing solid solubility with falling temperature, the theory of coherency hardening1 proposes that the principal source of hardening during precipitation is strain caused by coherency between the matrix and precipitate. For a given system greater coherency hardening would result from lengthening the period of coherent growth and/or increasing the number of nuclei, other things remaining equal. However, the hardness change during aging is a function of a number of phenomena in addition to coherency hardening, such as dispersion hardening, loss of coherency, solute depletion, matrix recovery or recrystal-lization, coalescence, and their relative time sequences. The present investigation was undertaken to study the effect of ternary additions on the age-hardening of Cu-Ag alloy. For this purpose a series of alloys were made containing as ternary constituents Mg, Al, Si, P, Mn, Ni, Zn, As, In, and Sb. These elements were added to a master 5 wt pct Ag in Cu alloy in such amounts as to obtain alloys listed in Table II containing the following approximate atomic percentages: 96 pct Cu, 3 pct Ag, 1 pct ternary addition. A 97 atomic pct Cu, 3 atomic pct Ag alloy was used as a comparison standard. There have been numerous investigations of age-hardening in Cu-Ag alloys2-lo but few of ternary Cu-Ag alloys. Pfister and Weist" found that 1 wt pct Ni reduced the solubility of Ag in Cu above 600 °C and that the rate of precipitation was slower than in polycrystalline Cu-Ag alloys of similar silver content. More recently Hodge, Jaffee, Dunleavy, and Ogden12 investigated the effect of ternary additions of Mg, Li, P, Cd, Zn, Zr and Be on strength properties of Cu-Ag alloys. Mg, Cd, and P were found to increase strength in the aged and cold-worked condition. Experimental Procedure Charges weighing 7.5 lb were melted in a closed carbon crucible under a reducing atmosphere* of nitrogen and hydrogen. A Durville-type casting procedure with a hot-top arrangement was used to obtain a sound casting, 2x2x43/4 in. Prior to rolling and annealing of the ingots, a trial solution anneal of rolled sections of the hot-top portions indicated that at 780°C melting was avoided except for the Cu-Ag-Sb alloy. This alloy could not be produced as a single phase within the limits of temperature control. i 3" to 5oC, since melting occurred at 64O °C, and below this temperature precipitation was

Jan 1, 1952

By I. Lowthian Bell

THERE has been probably no improvement introduced into the manufacture of iron which created more surprise in the minds of practical smelters and of scientific men than Neilson's discovery of the hot blast. In 1829, Messrs. Dunlop & Co. consumed at the Clyde Works, near Glasgow, nearly 79 tons of coal to make a ton of pig iron, of which about 20 cwts. was employed under the boilers of the blowing engines, leaving nearly 7 tons for the consumption of the furnace itself. In the year 1833, by heating the air to 612' F. (322' C.), they redoccd the 79 tons to 3 tons by the mere burning of 8 cwts. of coal in the apparatus for raising the blast to this temperature. The statenlent just given is strictly true in a commercial sense, but when we come to consider the question as one of physical science, it is necessary to eliminate some of the conditions which conduced to so extraordinary a result. Anterior to Neilson's time the fuel employed in smelting iron was coke, and it was supposed at that period, erroneously, however, that coal in its raw state, when burned with cold air, was totsally unfit for the purpose in question. This mineral, as it was obtained from the Lanarkshire coal-field, contained about 35 per cent. of volatile matter, but the process of charring it was performed in so unskilful a manner that instead of receiving 88 cwts. of coke from 135 cwts. of coal, 60 cwts. only was the product of the operation. Again, the reduced colisumption of carbon in the furnace itself was accompanied by a corresponding diminution of blast, and this was followed by an economy of half a ton in engine coal. After making a proper allowance, however, for all these collateral circumstances, we are within the mark when we admit that in actual coke, which is really the form the fuel has to assume before it is burnt in the blast-furnace, not less than 30 cwts. was saved by heating the blast to 615° F. (322° C.). This unexpected economy, be it remembered, was obtained by the combustion of the 8 cwts. of coal, somewhat wastefully applied in the hot-air apparatus. Numerous have been the opirlions advanced by different authorities in the scientific world to account for the apparent anomaly, bat none,

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By Bruce F. Grant, Stefan F. Szasz

During 1947, a Sinclair research team was assigned to investigate thermal methods of oil recovery. The assignment was recommended by a survey of possible research approaches to increase the amount of oil that ultimately can be recovered from oil producing reservoirs. The use of heat to stimulate oil production rates by the melting of paraffin deposited in well bores can be traced back to within one or two decades of the drilling of the Drake well. The application of heat on a larger scale has been discussed by generations of oil producers. Shortly after the turn of the century, one intrepid operator is reported to have injected steam into a Pennsylvania property. After a few weeks, he apparently became discouraged and terminated his experiment. Subsequently, the literature contains references to several well-developed techniques for supplying heat to a producing well bore to melt paraffin or to reduce the viscosity of oil contained in the formation immediately around the well bore.1.?.3.4 Some early references discuss procedures to furnish heat to the reservoir,5,6 with the injection well as the heat source, thus obligating the process to maintain the entire rock mass at a temperature above that at which the desired improvement in oil recovery would occur. Another approach to reservoir heating was reported by a group of Russian technologists in 1935.7,8,9 They definitely demonstrated that combustion can occur within the porous structure of an oil-bearing sandstone. Their field experiments, however, relied less on combustion within the rock than on heat furnished by combustion of oil supplied to the injection well bore. Ignition of the air-oil mixtures in the well bore was found very difficult, and the field tests were carried on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well, on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well. The Brundred Oil Corp. reportedly obtained combustion in the sand immediately around the injection well bore, but the experiment was abandoned because of interference with normal production schedules. Injection capacity of the experimental well was greatly reduced by firing. The well was reshot and pieces of sand showing partial fusing of the quartz matrix were recovered. To the authors' knowledge no other field experiments utilizing combustion techniques for formation heating were undertaken prior to 1948, although the patent literature evidences continued interest in formation heating."'," CONCEPT OF COMBUSTION-SUPPORTED HEAT WAVE The references cited were in agreement that heat applied to a reservoir would increase recovery, but there

Jan 1, 1955

By F. E. Wood, H. W. Young, A. W. Buell

This paper summarizes the results of laboratory tests conducted to determine the properties of the paraffin or rod-wax encountered in the Salt Creek field, Wyoming. It also describes field tests and methods employed to cope with the paraffin problem. The conclusions to bo drawn from the laboratory work are: 1. Samples of Salt Creek paraffin range in consistency from soft lo hard, the melting points varying from 120" to 156" V. 2. Masses of soft paraffin are soluble to an appreciable extent in crude oil and its liquid fractions at temperatures somewhat below the melting point of the paraffin. Hard paraffin is very slightly soluble. under these conditions. 3. Agitation apparently increases the amount of paraffin that will go into solution. 4. Paraffin congeals from solutions upon cooling to the point of saturation ation, which is in all cnscs below thc melting point of the paraffin. 5. Crutltl oil is tlie most effective. of all the solvents for holding paraffin in solution. 6. Pressure alone does not appreciably affect the solubility of paraffin in crude oil nor does it aid materially in holding paraffin in solution when the temperature is reduced. 7. Natural gas in solution under pressure does not appreciably increase the solubility of paraffin in crude oil, hut is effective in holding paraffin in solution when the temperature is reduced. 8. A foreign body introduced into a solution of paraffin in oil is imrnediately coated with paraffin if the temperature of the solution is at or below the melting point of the paraffin, and the object is considerably cooler than the solution. It may not be entirely correct to ray that paraffin is taken into solution; it is impossible that the paraffin may be in suspension rather than in solution.

Jan 1, 1928

By Evan Bennett

ALMADEN is Arabic for "the mine." The definite article is properly used, for no mercury mine in the world compares with it for richness and volume of ore, produced and potential. After more than twenty centuries of exploitation, intensive throughout the last lour, ore from Almaden is about five times as rich as that of its closest competitor. We drove to the mine one April afternoon, across Don Quixote's plains of the Mancha, up the bleak, arid valley of the Rio Valdeazogue where we passed tenth century Moorish workings and their ruined castles. At dusk, we came to the Hacienda de Castilseras, a large farm where Almaden miners work their land on off days. Then we drove through the whitewashed, well-ordered town to the Castillo de la Direccion where we were challenged at the iron gate by two picturesquely costumed Guardias Jurados.

Jan 1, 1948

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By A. M. Gaudin, F. W. Bowdish

MINERAL dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,7 its magnetic remanence,3 the turbidity of its suspension,8 and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid-both internal and external-the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample .2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. APPARATUS In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. 1 and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1944

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By Byron M. Bird

JIGGING is the stratification of a mass of solid particles in upward pulsations of water or in alternating upward and downward pulsations. The stratification usually is effected in a rectangular open-top container having a perforated bottom through which the pulsations of water are applied to the materials to be separated; in separating coal, to a mass of coal and refuse. Jigging usually is a continuous process involving three steps: (1) the reception of the raw coal, (2) the stratification of the coal and refuse so that the refuse settles to the screen plate, and (3) the overflow of the cleaned coal and the withdrawal of the refuse collected on the screen. The jig is the most universal washer ever devised. It is handling in practice a wide range of closely sized coals and ores, mixed sizes of coal from 8-in. to 0 through ¾ -in. to 0, and mixed sizes of ores down to 7/32-in. to 0 and even smaller. It is treating materials ranging in specific gravity from that of gold at 19 to that of coal at 1.30. It is handling feeds in which the proportions of high-gravity materials range from 90 per cent or higher, as for some iron ores, to 10 per cent or less for some coals. It is handling feeds containing all shapes of particles-round, rectangular, and , flat. It is handling simple separation problems and difficult separation problems. Thus, it is an almost universal separating device. One might add that it has been one of the most misunderstood types of washers, from both a theoretical and a practical point of view. Although considerable progress has been made in coal jigging in the past 10 years, the jig probably has more unexplored possibilities than any other type of washer. In this chapter the object has been to treat the jigging process in a practical manner and to give information that will help the reader to improve his particular operation. Inasmuch as performance data from operating plants would contribute little of value, none has been given. Instead, the emphasis is upon jigging principles as a foundation for attacking the problems that arise. These principles are in reality tentative conclusions from research in the field of jigging during the past 10 years and most of this chapter should be regarded as a progress report on an investigation still under way. As all really difficult problems in jigging arise from an attempt to treat a large range of sizes in one operation, nearly the entire discussion will be

Jan 1, 1943

By Robert T. Howard, Morris Cohen

THE purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature trans- formations have been summarized recently by Troiano and Greninger.1 Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation [(M,)] during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transfoi mation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metallographic3 and dilatmetric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Steward7 have shown that the Greninger-Troiano metallographic techniques may be used not only for [M,] determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below [M,] in fourteen commercial steels. In the present paper, the Greninger- Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M,, thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. EXPERIMENTAL DETAILS Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M, temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1947

By Carl L. Shapiro, Jerome and Strauss

This is a critical examination of the theory that the amount of carbon necessary to form the iron-carbon (carbide) eutectoid is lowered by the addition of any carbide-forming element. Although this theory has been built up over a long period of years, it appears, in the light of recent published investigations upon the ternary constitutional diagrams of iron with carbon and other alloying elements, to be no longer tenable. A survey of these new results, summarized below, shows that (as is known) some metals lower the carbon content of the iron-carbon (carbide) eutectoid, whereas others raise it, but (as not heretofore clearly set forth) some first move the eutectoid in one direction and then, at higher concentrations, shift it in the opposite direction. Moreover, these differences in behavior exist even among the common alloying metals classed as carbide formers. PART I Influence of Body-centered Cubic Elements The effects of the various body-centered cubic metals (chromium, tungsten, molybdenum, vanadium, columbium and tan. talum) are reviewed individually. Iron-carbon-chromium System.—In the monograph on Alloys of Iron and Chromium, Kinzel and Crafts1 concluded that the carbon content of the eutectoid is lowered by increasing the chromium content. The quantitative influence of chromium on the eutectoid point of iron-carbon alloys was shown by Monypenny2 (Fig. I) and no data have been forthcoming to refute his findings. Iron-carbon-tungsten System.—Gregg,3 in the monograph on Alloys of Iron and Tungsten, accepted the data showing that tungsten decreases the amount of carbon required to form the eutectoid. The influence of tungsten on the eutectoid percentage of carbon as determined by Oberhoffer and Daeves4 is shown in Fig. 2; these results have received general approval. , I ron-carbon-molybdenum System.—In the monograph on Alloys of Iron and Molybdenum, Gregg5 reviewed the work of Guillet,6 Swinden,7 and ReedI8 all showing that molybdenum lowered the carbon content of the eutectoid, whereas Takei9 contradicted this conclusion. Svetchnikoff and Alferova,10 a little later, showed that large additions of molybdenum shift the eutectoid to the right. These last-named investigators found that molybdenum, up to 1.2 per cent, shifts the pearlite point and the point of maximum solubility of cementite in the gamma phase only slightly in the direction of lower carbon content; on the other hand, increasing amounts of molyb-S

Jan 1, 1944

By Jerome and Strauss, Carl L. Shapiro

This is a critical examination of the theory that the amount of carbon necessary to form the iron-carbon (carbide) eutectoid is lowered by the addition of any carbide-forming element. Although this theory has been built up over a long period of years, it appears, in the light of recent published investigations upon the ternary constitutional diagrams of iron with carbon and other alloying elements, to be no longer tenable. A survey of these new results, summarized below, shows that (as is known) some metals lower the carbon content of the iron-carbon (carbide) eutectoid, whereas others raise it, but (as not heretofore clearly set forth) some first move the eutectoid in one direction and then, at higher concentrations, shift it in the opposite direction. Moreover, these differences in behavior exist even among the common alloying metals classed as carbide formers. PART I Influence of Body-centered Cubic Elements The effects of the various body-centered cubic metals (chromium, tungsten, molybdenum, vanadium, columbium and tan. talum) are reviewed individually. Iron-carbon-chromium System.—In the monograph on Alloys of Iron and Chromium, Kinzel and Crafts1 concluded that the carbon content of the eutectoid is lowered by increasing the chromium content. The quantitative influence of chromium on the eutectoid point of iron-carbon alloys was shown by Monypenny2 (Fig. I) and no data have been forthcoming to refute his findings. Iron-carbon-tungsten System.—Gregg,3 in the monograph on Alloys of Iron and Tungsten, accepted the data showing that tungsten decreases the amount of carbon required to form the eutectoid. The influence of tungsten on the eutectoid percentage of carbon as determined by Oberhoffer and Daeves4 is shown in Fig. 2; these results have received general approval. , I ron-carbon-molybdenum System.—In the monograph on Alloys of Iron and Molybdenum, Gregg5 reviewed the work of Guillet,6 Swinden,7 and ReedI8 all showing that molybdenum lowered the carbon content of the eutectoid, whereas Takei9 contradicted this conclusion. Svetchnikoff and Alferova,10 a little later, showed that large additions of molybdenum shift the eutectoid to the right. These last-named investigators found that molybdenum, up to 1.2 per cent, shifts the pearlite point and the point of maximum solubility of cementite in the gamma phase only slightly in the direction of lower carbon content; on the other hand, increasing amounts of molyb-S

Jan 1, 1944

By T. L. Joseph

Sulfur balances calculated from operating data covering thirty-five blast furnaces indicate that approximately 92 per cent. of the total sulfur charged enters with the coke, 7 per cent. with the ore, and 1 per cent. with the stone.. Most of the sulfur is carried from the furnace by means of the slag, the total amount eliminated being the product of the slag volume and the percentage of sulfur it contains. Additional sulfur in the charge must be eliminated either by increasing the percentage of sulfur in the slag or the quantity of slag. From relations found between slag volume and coke consumption and sulfur in the coke and slag volume, curves have been prepared showing the relative value of blast-furnace coke as its sulfur varies from 1 per cent. CHARCOAL was the predominant blast-furnace fuel until 1838, when it was found, by the operation of a 2-ton experimental furnace, that anthracite could also be used. This information was a stimulus to the iron industry, particularly in eastern Pennsylvania where anthracite was available at low cost. The production of anthracite pig iron increased steadily and, in 1855, its tonnage exceeded that of charcoal iron. Of the 680 furnaces in operation in 1874, the 226 using anthracite produced nearly one-half the total tonnage. In 1869, the production of coke furnaces exceeded that of charcoal furnaces and, in 1875, coke surpassed anthracite as a metallurgical fuel. In 1907, the output of anthracite pig dropped well below a million tons and its present significance is largely historical. In recent years, the production of coke has gone hand in hand with the production of pig iron and it has gradually attained the position it now occupies as a universal blast-furnace fuel. Charcoal, however, has great merit as a blast-furnace fuel chiefly because of its freedom from ash and sulfur. The harmful effect of the latter and the necessity of keeping the percentage of this element in pig iron at a minimum are well recognized. Other contaminating elements can be reduced to specified limits in the steelmaking process, but the control of sulfur belongs essentially to the blast furnace. The purpose of this paper is to point out the distribution of this impurity in blast-furnace

Jan 9, 1924

By L. A. Geoffrion, R. H. Perkins, J. C. Biery

Densities of cerium metal and several lour-melting binary cerium alloys were measured over the range 25° to 800°C. A rolumeter, using NaK as working fluid, was used to obtain the data. The cerium, Ce-Co, Ce-Ni, and Ce-Cu alloys all exhibited an increase in density on melting, while a Ce-Mn alloy expanded on melting. FOR the proper design of a nuclear reactor, the change in density of the fuel with temperature must be known. This is especially important in a system utilizing molten fuel, such as LAMPRE (Los Alamos Molten Plutonium Reactor Experiment), since a relatively large change in density usually occurs during the solid-liquid transition. The fuel for LAMPRE is a Pu-2.5 wt pct Fe alloy with a melting temperature of 410°C. However, limitations in reactor design with this fuel have led to consideration of other plutonium-containing alloys for use in future generations of this type of reactor. Several ternary alloys containing plutonium and cerium as two components have satisfactorily low melting points. The system that at the present time appears to be most acceptable is Pu-Ce-Co; it exhibits little change in melting temperature with wide variation in plutonium concentration. Other alloys that have received some consideration contain nickel, copper, and manganese as the third constituent. The proposed fuel alloys are difficult to handle experimentally in the 25" to 800°C temperature range since they oxidize readily, react with many solvents, and contain a poisonous fissionable material. In addition, in this temperature range the alloys pass through the solid-liquid transition. Several techniques are available for measuring the densities and volume coefficients of expansion of solids or liquids. However, the only apparatus that appears suitable for measuring expansion coefficients over this temperature range and through the phase transition is a volumeter. In a volumeter, the indicating medium must be essentially inert to and insoluble in the material being studied. It must also possess a low vapor pressure over the operating temperature range, and its coefficient of expansion must be accurately known. One material that is satisfactory in nearly all of these respects is the alloy Na-78 wt pct K, which melts at -10°C and has a vapor pressure of 860 mm Hg at 800°C. This relatively high vapor pressure at 800°C requires an overpressure of an inert gas to prevent boiling. While a volumeter is capable of determining accurately the volume coefficients of expansion of materials, it cannot be used for absolute density measurements. Therefore, a density determination at a known temperature must be coupled with the volumeter measurements to give all the desired data. The weight-loss technique using immersion in bromobenzene at room temperature proved to be satisfactory. The preliminary work that was done on this experimental program involved developing and calibrating the equipment, and measuring the densities and volume coefficients of expansion of cerium and some low-melting binary cerium alloys. The complications that are caused with the introduction of plutonium into the system were avoided until the equipment was proved to be satisfactory and until experience was gained in its operation. It is this first phase of the experimental work that is described in this report. DESCRIPTION OF EQUIPMENT AND OPERATING PROCEDURE The NaK volumeter is shown schematically in Fig. 1. Basically, the equipment consists of two weld-sealed stainless-steel containers of nearly identical volume. One container holds a tantalum crucible and the specimen being measured; the other contains a tantalum crucible and a tantalum specimen used as a control reference material. To avoid temperature gradients, the bombs are located in a copper block inside the furnace. Stainless-steel capillaries of equal length and volume connect each stainless-steel container to a glass viewing capillary. The stainless-steel containers, stainless-steel capillaries, and a portion of the glass capillaries are filled with NaK (22 wt pct Na-78 wt pct K). The NaK/gas interface in the glass capillary is viewed with a cathetometer which is accurate to *0.5 mm. The cathetometer readings are used to calculate the volume changes of the samples during a run. This volumeter is basically the same as that described by F. Knight in Plutonium 1960. 2 However, changes in equipment design and operating procedure were made to eliminate some major operating difficulties. These changes are summarized below. 1) In filling the manometer with NaK, gas was frequently entrained in the system. Evacuation of the system before filling failed to eliminate the en-

Jan 1, 1965

By H. P. Moore, R. W. Fenn, Harold Margolin, W. R. Hibbard

DEFORMATION lines, also called etch markings or strain markings, are noneffaceable lines developed in individual grains by etching a metal specimen which has been cold worked sufficiently to cause atomic non-conformity or slight orientation differences within the grains. Etching occurs more rapidly at these lines of high chemical reactivity to produce a result similar to that revealing grain boundaries.1 Wider etching effects forming bands have been found. They are believed to be bands of deformation lines which form areas of measurably different orientation from the crystal matrix. The crystallite rotations causing these bands have been shown by Barrette to contribute to deformation textures. Although deformation lines have been observed in many metals, the amount of deformation required for their appearance has been established only in general terms. Mathewson and Phillips3 observed the first appearance of deformation lines in cold-rolled alpha brass at about 20 pct reduction in thickness using the standard ammonium hydroxide hydrogen peroxide etchant. Price and Davidson4 noted deformation lines in common high brass after 26.5 pct reduction by cold rolling using the same etchant. Johnson' observed dark thick forklike lines in 99.99 pct pure copper reduced 31.8 pct. Adcock6 observed deformation lines in 80-20 copper-nickel alloy rolled 50 pct. Samans7 found no deformation lines in alpha brass single crystals cold rolled 9.5 pct but they did appear after 25 pct reduction using ammonium hydroxide and hydrogen peroxide etchant. Barrett and Levenson8 observed deformation bands in drawn polycrystalline iron at very small reductions in area and noted that their initial appearance perhaps depends on grain size and other conditions. They reported deformation bands in a single crystal of iron reduced 6 pct by drawing. Brick9 noted that deformation lines in 70-30 brass apparently associated with {111} planes appeared after reductions of from 20-50 pct by cold rolling. Brick and Williamson10 noted that in single crystals of 70-30 alpha brass "as in polycrystalline brass, no deformation markings appeared until reductions exceeded 20 pct." Cook and Richards11 reported that in copper cold rolled less than about 50 pct few strain markings were apparent but for higher. reductions many strain markings appeared transverse to the rolled direction. In a review article Brick and Phillips12 noted that previous studies had not shown deformation lines in cold rolled alpha brass

Jan 1, 1948

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood' suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener's mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh's5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By Leonard B. Griffiths

In a recent communication, Smith and Wood described some results of 800°C compression/creep tests on WC-12 wt pct Co alloys in which plastic flow in the WC particles was believed to have occurred. The deformation observed in the WC particles was found to be a function of the rate of loading. The authors suggested that their data constituted support for the Ansell6-Lenel theory of yielding in dispersion-strengthened alloys. I do not agree with this interpretation since the Ansell-Lenel theory does not apply to the type of alloy in question. In this alloy, the dispersoid is present to the extent of about 80 vol pct. Even where there is no continuous skeleton, which apparently is the case in this instance, the simple fact is that nearly all of the load is carried elastically by the stronger material (wc).7 The constraint imposed upon the matrix, by virtue of the differences in Young's modulii and Poissons ratios, severely limits the stress level to which it may be subjected (assuming that the interfaces remain intact). If one allows for the constraint and then performs the same computation as in Smith and Wood, one finds that the stress on a WC particle is about 4 x 105 psi. This is about 21/2 times lower than the predicted fracture stress for WC. I would completely agree with the final paragraph of Smith and Wood, namely, that loading rate is of considerable significance. However. a more likely interpretation of their data is, I submit, that in the absence of stress relaxation (by secondary slip or climb) those WC-Co interfaces subjected to a normal tensile stress begin to fail. Once this occurs, the stress distribution will change rapidly and "premature" fracture of the WC then becomes quite probable. Tne serrated edges shown in Fig. 1 may very well be fine, interface fissures.

Jan 1, 1970