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By A. H. Larson, T. P. McNulty

RECENTLY, an investigation of the absorption of sulfur dioxide gas in molten binary copper alloys was conducted. A Sieverts-type apparatus, consisting of a mercury-filled gas dispensing buret and a mercury manometer, was used initially for determining the volume of gas absorbed as a function of pressure. The equilibration behavior of the alloys studied indicated that the mercury in the gas measuring system was absorbing sulfur dioxide. Owing to the widespread use of mercury as a displacement medium in absorption studies, an investigation was made to determine the nature and magnitude of the mercury - sulfur dioxide absorption effect. The gas measuring system was modified by substituting a Worden Quartz Products Type PDHV fused-quartz-spiral pressure gage for the mercury-filled dispenser and manometer. The dispensed gas volume at known temperature and atmospheric pressure was measured by evacuating a Pyrex vessel of known volume and by admitting sulfur dioxide into the vessel until the attached quartz pressure gage registered atmospheric pressure. Atmospheric pressure was measured concurrently with a separate mercury barometer. The volume of the empty sample chamber and its attendant apparatus was determined by measuring the equilibrium pressure accompanying the addition of a measured volume of sulfur dioxide into the initially evacuated system. The volume of the mercury sample was calculated from the density of mercury at the temperature of the study (25°C). Measured volumes of sulfur dioxide were then dispensed into the system and the equilibrium pressure accompanying each gas addition was determined. From the difference between the system volume and the mercury volume, the number of moles of gaseous sulfur dioxide remaining in the system at each pressure was calculated. The difference between the number of moles of gas dispensed into the system, denoted Enso2: and the number of moles of gas remaining in the system after absorption equilibrium had been attained, denoted nso2(g), was equal to the number of moles of absorbed gas, denoted nSO2. The number of moles of absorbed gas was then converted to absorbed volume, denoted VSo2, in cu cm at stp conditions of (PC and 760 mm Hg. Table I contains calculated values of Snso2, nSo2(g), and VSo2 for different sulfur dioxide pressures. In the original system, denoted Run I, volume limitations of the gas dispensing system prevented absorption studies at equilibrium pressures near atmospheric pressure, so a different gas dispensing system, denoted Run 11, was used for determining the last pressure reading in Table I. The data in Table I are expressed in terms of the absorption of sulfur dioxide in 49.68 cu cm of mercury. In Fig. 1, these data are expressed in terms of the absorption of sulfur dioxide in 100 cu cm of mercury. Since the absorption data plotted in Fig. 1 show a linear relationship, the volume of sulfur dioxide absorbed in mercury is a function of the first power of pressure. The absorption reaction is So2(gas) = SO2 (in Hg) The first-power pressure dependence, coupled with the fact that the sulfur dioxide could be removed from the mercury by applying vacuum, indicated reversible

Jan 1, 1967

By W. L. Remick

The hydrotator coal-cleaning process was developed as an economic necessity to meet the ever-increasing demand for an inexpensive method of cleaning coal down to the sizes ordinarily referred to as "dust." As the most urgent demand seemed to be in the anthracite field, all experimental work has been conducted in that territory during the past two years, with the exception of a few months during the strike of 1925-26, when some experiments were performed in the Alabama bituminous fields. The first commercial plant was constructed at the Middle Creek Colliery of the Philadelphia & Reading Coal & Iron Co.,. Pottsville, Pa. This plant is now operating. Application The field of application of the process is: 1. Cleaning anthracite fines, ordinarily described as "slush" or "silt." Slush contains all sizes from 3/32 in. down to and including I(dust." (Anthracite passing a 3/32-in. mesh is also referred to as No. 2 Barley and No. 4 Buckwheat.) 2. Cleaning sizes too fine for recovery by other methods. 3. Removal of coal from sand circulated in the Chance sand-flotation process. 4. Cleaning of bituminous sizes from % in. down to "dust." 5. As equipment for the performance of the froth flotation process. 6. Other separating, extraction and washing processes which may be considered outside the realm of coal cleaning. Principle of Operation Fig. 1 shows the method of classification practiced under the Hydrotator patent.' In coal cleaning the machines are operated as "hindered settling" classifiers, the flow of solids and liquids being so controlled that the units may be combined in series.

Jan 1, 1927

By M. W. Burkart, B. Lustman

Uranium-base alloys exposed to high temperature water fail either by uniform oxidation or by sudden cracking and disintegration of the metal. The disintegration results from the oxidation of a second phase which is precipitated during the corrosion process. The precipitate has been identified as a metastable hydride of uranium. URANIUM-BASE alloys consisting of the body-centered-cubic ? phase are susceptible to two different modes of corrosion failure when exposed to high temperature water. In the first process, a smooth oxide film is formed on the metal surface which continually flakes off during exposure and results in a uniform weight loss of the specimen. The oxide is present as a thin, adherent layer whose thickness remains approximately constant. As the metal oxidizes during corrosion, a nonadherent layer is built up on this film and continually sloughs off. Coincident with the uniform corrosion just mentioned, another process occurs which eventually leads to failure of the metal by cracking and general disintegration. The failure takes place during a relatively short time compared to the total exposure. To distinguish this type of failure from the uniform corrosion, the cracking or disintegration of the metal will be referred to as discontinuous failure. For the ? phase uranium alloys it is discontinuous failure rather than uniform corrosion that limits the useful corrosion life of the alloy. This paper will be concerned primarily with the mechanism of discontinuous failure. Physical Changes During Corrosion—The alloys used in this investigation were ? phase uranium alloys containing 7 to 12 wt pet Mo or Cb. The preparation of the alloys, the method of corrosion testing, and the actual corrosion results are presented in another paper.' The ? quenching treatment consists of annealing the alloy for 24 hr at 900°C in a sealed Vycor glass tube filled with helium and then water quenching to room temperature without breaking the tube. The corrosion behavior typical of a ? phase uranium alloy is shown in Fig. 1. This specimen was a U-12 wt pet Mo alloy tested in pressurized, degassed water at 650°F. The corrosion rate was practically constant at 0.28 mg per sq cm per hr or increased slightly until about 15 to 20 days of exposure, when the onset of discontinuous failure occurred in this particular sample, and the specimen soon began to crack and disintegrate. The simultaneous increase in the observed corrosion rate is a result of the increased area of exposure due to cracking of the specimen. The microstructure of a specimen that failed by cracking is shown in Fig. 2. The presence of a plate-like precipitate can readily be seen. Metallographic examination of corrosion specimens reveals that the onset of discontinuous failure is always preceded by the formation of a plate-like second phase in the ? uranium matrix. Hydrogen analyses of specimens periodically withdrawn from corrosion test reveal that the hydrogen content of the alloy increases on exposure to the high temperature water, as shown in Fig. 3. The hydrogen is available as a corrosion product resulting from the formation of UO2 by the reaction of the alloy with water. Specimens analyzed just prior to discontinuous failure contained as much as 1200 ppm H, whereas the plate-like phase appears to precipitate out at a hydrogen concentration of between 10 and 25 ppm. The observed increase in hydrogen content prior to and during the formation of the plate-like precipitate suggests that this constituent may be a hydride of uranium. Additional evidence linking the identity of this phase to a hydride is that it can be removed by vacuum annealing at temperatures of 100°C and above. Decomposition products of the ? phase would certainly not dissolve at such temperatures, nor could other likely products of corrosion, such as oxides, be dissipated at any of the test temperatures. The precipitation and growth of the second phase during corrosion is accompanied by an increase in hardness of the specimen. The hardness increase results from the dispersion of the harder precipitated

Jan 1, 1959

By William Kent

More than twelve years were spent by Wöhler at the instance of the Prussian Government in experimenting upon the resistance of iron and steel to repeated stresses. The results of his experiments are expressed in what is known as Wöhler's law, which is given in the following words in Du Bois's translation of Weyrauch:* " Rupture may be caused not only by a steady load which exceeds the carrying strength, but also by repeated applications of stresses, none of which are equal to the carrying strength. The differences of these stresses are measures of the disturbance of continuity, in so far as by their increase the minimum stress which is still necessary for rupture diminishes." A practical illustration of the meaning of the first portion of this law may be given thus: If 50,000 pounds once applied will just break a bar of iron or steel, a stress very much less than 50,000 pounds will break it if sufficiently often repeated. This is fully confirmed by the experiments of Fairbairn and Spangenberg, as well as by those of Wöhler; and, as is remarked by Weyrauch, it may be considered as a long-known result of common experience. It partially accounts for what Mr. Holley has called the " intrinsically ridiculous factor of safety of six." Another "long-known result of experience"—although this has not, as the writer believes, been investigated by scientific experimenters—is the fact that rupture may be caused by a succession of shocks or impacts, none of which alone would be sufficient to cause it. Wrought iron will crystallize by repeated blows in service and become weaker than cast iron. Iron axles, the piston-rods of steamhammers, and other pieces of metal subject to continuously repeated shocks invariably break after a certain length of service. They have a "life" which is limited. Iron rods in bridges sometimes crystallize and break, although the rods in most of our iron bridges

Jan 1, 1880

By A. Karim, T. G. Langdon, C. Y. Cheng, J. E. Dorn

The effect of changes in temperature and stress on the creep behavior of Fe-4 pct Si was investigated over the temperature range from 650° to 1175K Over the temperature range of 799° to 110l°K, the shear strain rate, ?', obeys the relationship: where K is a constant, 7 the applied shear stress, G the shear modulus, g the free activation energy for diflusion, R the gas constant, and T the absolute temperature. The results strongly suggest that the creep in this alloy is controlled by a dislocation climb mechanism. In a recent investigation, Ishida, Cheng, and Dorn1 observed that the apparent activation energy for creep of a! Fe from 480" to 775°K corresponded to that for self-diffusion. Over the magnetic transformation range (775" to 1045"K), the apparent activation energy for creep increased steeply with increasing temperature in agreement with the known decrease in the free activation energy for self-diffusion. Passing through the Curie temperature, the apparent activation energy decreased abruptly following which it then increased mildly as the temperature further increased. Inasmuch as the apparent activation energy for creep of a! Fe below the Curie transformation range of temperatures appeared to decrease with increasing values of the stress, the data were analyzed in terms of a model based on the nonconservative motion of jogged screw dislocations. But since the observed creep rate was much higher than that which could be accounted for on the basis of usual models, the authors found it necessary to assume that pipe diffusion became significant over the lower temperature range. Furthermore, the abnormally high activation energy for creep above the Curie temperature was attributed to grain boundary migration which became prevalent in this temperature range. It was thought that a number of the interesting issues that arose in the creep of a Fe might be resolved by investigating the creep of Fe-4 pct Si alloy: This alloy has about the same Curie range and therefore should give creep results that closely parallel those for a Fe and in this way provide comparable data for analysis of creep mechanisms. Furthermore, it can be annealed at higher temperatures which could provide some stabilization against grain boundary migration. In addition, it might serve to illustrate the possible effects of short-range ordering on creep.

Jan 1, 1969

By Frank Firmstone

In the Kaernthner Zeitschrift, No. 2, 1881, p. 53, et seq., Prof. Ledebur details some experiments on the power of various silicates of lime and alumina, magnesia and alumina, and lime, magnesia and alumina, to remove sulphur from pig-iron, from which it appears (as has long been recognized in practice) that the more basic the silicate the greater the quantity of sulphur it will take up; but also that for the same grade of silicate, this quantity is greatest for the lime-alumina silicate and least for the magnesia-alumina silicate, the lime-magnesia-alumina silicate occupying an intermediate position, and he concluded therefrom (p. 59) that, for the production of pig-iron low in sulphur, pure limestones are to be preferred to those containing magnesia. Much the same opinion has been published elsewhere on high authority, and lately (not to multiply references) by Sir Lowthian

Jan 1, 1895

By C. R. Hayward

THE CHAIRMAN (ALBERT SAUVEUR, Boston, Mass.).-I am sure we are indebted to Prof: Hayward for his addition to our knowledge of the influence of sulphur on steel. As he has said in this paper, sulphur has had many defenders in recent years. It seems to me, however, that, while it may be old school to believe in the detrimental action of sulphur, it is not yet old school to believe in segregation; that while it may be that 0.1 per cent. of sulphur has no very great effect on the physical properties of steel, a ladle analysis of 0.1 per cent. of sulphur may readily result in 0.2 or 0.3 per cent. sulphur being present in the segregated portion of the ingot, and that, it seems to me, might be a rather serious matter. J. S. UNGER, Pittsburgh, Pa.-Prof. Hayward has presented the results of an investigation along a line to which I have devoted considerable time and attention, and I am particularly pleased to note that his results are in accord with my own and further tend to prove the fact that the old, established prejudice against sulphur is based more on belief than actual facts. I have felt for years that tooo much stress was placed on the harmful influence of certain elements in steel such as sulphur, phosphorus, copper, etc., but it has only been within recent years that efforts have been made to, establish the truth. Practically all the investigations made to date have proven that these elements within reasonable limits are harmless and, in fact, that for certain purposes the addition of these elements is beneficial. In referring to copper, J. E. Stead, Vice-President of the British Iron and Steel Institute, said at their last meeting: "Even today one comes across steel specifications in which copper is barred, which can only be regarded as ail indication of ignorance, if not stupidity, of those who prescribe the composition of steel, for it has been long ago proved that copper in steel, instead of being an evil, is quite harmless, and is sometimes distinctly beneficial." Sulphur owes its evil name to the early days of the manufacture of steel. Chemical analyses were crude, and failure due to either poor raw materials or metallurgical treatment were many. Sulphur being a comparatively easy element to determine with reasonable accuracy, particular attention was called to the amount of sulphur, and the failure was attributed to it, without giving any consideration to other causes. A pre-

Jan 4, 1917

By W. E. Horst

John Dasher (Central Research Laboratory, Crucible Steel Co. of America, Pittsburgh. Pa.)— Getting spodumene to float quickly and cleanly can be a problem. The author has presented an excellent account of a valid and useful approach to the scale-up of such problem floats. This indicated advantages for doubling retention time, i.e., buying another set of flotation cells. The author states that 21 pct of the spodumene floated in 2 min in the laboratory cell, that the grade of the rougher was about 75 pct spodumene, and that the final tailing contained 4 to 12 pct spodumene in different sizes with the present cells and 1 to 9 pct spodumene with twice as many cells. About 20 years ago, this writer obtained in the laboratory the flotation of over 90 pct of this spodumene in a King's Mountain sample in 1 min at a grade of 90 pct spodumene in the rougher and a final tailing that contained only 1 pct spodumene. The methods of Norman, Ralston," and Gieseke' were used, which teach that spodumene floats quickly and cleanly if its surfaces have been properly conditioned chemically and/or mechanically prior to flotation. Although feed preparation is not discussed, the results reported indicate that it is inadequate. This writer suggests that improvements in this area might be more effective than doubling the number of cells. W. E. Horst (author's reply)—Dasher's comments are appreciated by the author and require some clarification. He suggests that improved spodumene flotation performance may be obtained by feed preparation techniques rather than increased retention time in flotation. Certainly flotation performance is dependent on feed preparation and this is an important feature in the flotation process. It is true that certain types of spodumene ores, particularly weathered ores, require more complicated feed preparation processing than clean ores to achieve the desired flotation results. It was not implied that current feed preparation techniques are the same as experienced during the scale-up investigations. Although discussion of feed preparation was omitted from the article on scale-up relationships, the important feature was that pre-treatment processing was the same for each level of operation investigated— laboratory, pilot plant, and plant scale. Under these similar conditions large differences existed in recovery for comparable time intervals in each scale of operation. It is highly probable that feed preparation techniques could be modified and thereby increase the flotation rate for each scale or all scales of operation discussed. However, modifications would have to be justified on an economic basis.

Jan 1, 1960

By Bradley Stoughton

As a part of the systematic study of the alloys of iron under the auspices of the Engineering Foundation, and preliminary to the commencement of comprehensive work on this larger subject, the authors have undertaken an investigation of the available literature dealing: with the alloys of iron and silicon. The purpose is to collect all the data in English and foreign languages and present them in two mono-graphs, one of a more scientific and the second of a more industrially useful nature. Of course, a great deal of information upon the constitution of the iron-silicon alloys was found specificially upon the changes of phase in the equilibrium diagram and the different phases present, such as solid solution, chemical compounds (iron silicides), etc. While no extended research was contemplated in the particular study undertaken, nevertheless the data collected proved to be so contradictory in many respects that a simple study of some of the outstanding problems involved in the constitution and equilibrium diagram was undertaken Because research was not a primary object of the work, and also because of the extreme industrial importance of the silicon alloys between 0.80 and 14 per cent. silicon, and finally because of the unsatisfactory state of knowledge existing as to these alloys, the experimental investigation was limited entirely to alloys with less than 10 per cent. silicon.

Jan 1, 1930

GRAHAM BRIGHT,* East Pittsburgh, Pa.-Bee-hive coke ovens are usually located at the mines, where the gases from the ovens are not strongly objectionable because the communities are not thickly built up. The byproduct oven will naturally he located near centers of industry, to which the coal can be brought from different directions and desirable mixtures can be made; where also the byproducts can be readily marketed, while the gas can be utilized for industrial and domestic purposes. Not much thought seems to have been given to the gases escaping from the byproduct coke oven, which are more or less objectionable in thickly populated sections. When the byproduct oven shall have been more widely installed, this question is likely to become serious, and it will be necessary to apply remedies. May I ask what has been done, or is going to be clone, in this direction? S. A. Moss, ? Lynn, Mass.-One cause of escaping gas is that the gas exhausters do not supply the proper suction. If a satisfactory regulating governor is applied and the correct kind of gas exhauster is used, the trouble will be eliminated. J. I. THOMPSON,? Pittsburgh, Pa.-The hoppers Co. has made a careful study of the question of smoke prevention. The smoke caused by the operation of the byproduct coke ovens is infinitely less than that caused by bee-hive ovens.

Jan 11, 1918

By H. Ries, R. E. Somers

Bodies of pyritic ore in schistose rocks have long been known in different parts of the world. The several occurrences resemble each other in being usually of more or less lenticular shape, inclosed in walls of schist or gneiss, and carrying pyrite, chalcopyrite, and pyrrhotite in varying proportions, as the chief ore minerals. The deposits differ, however, in that sometimes one, sometimes another, of the three sulphides mentioned may predominate. The orebodies in general are more or less closely conformable with the schistosity of the wall rocks, although in cases this may not hold true. The boundaries may or may not be sharp, but in general are fairly distinct. The lenses vary in size, may occur singly, or in groups; in the latter case they may be in line, overlapping, or occasionally parallel. Pinching and swelling of individual lenses is not uncommon. The genesis of these pyritic bodies has provoked much discussion, and they have been variously classed as sedimentary, igneous intrusions, hydrothermal replacements or impregnations, etc. Indeed, in some cases different geologists have most positively assigned widely diverse origins to the same deposit, as in the case of Rio Tintol and Rammels-berg.2 It is true that in the light of modern criteria, we have been able in a few cases to decipher clearly the process of origin and so there seems no. doubt now regarding the genesis of the deposits at Rio Tinto, Spain;3 Rammelsberg, Germany;4 Ducktown, Tenn.;5 southwestern Virginia;=

Jan 1, 1918

By G. A. Josey, T. P. Floridis

INFORMATION on the effect of alloying elements on the solubility of sulfur in solid iron alloys is limited to the effects of carbon,' manganese,' and Silicon.Refs. 3 to 5 provide information on the combined effects of silicon and manganese also. In the investigation reported in this communication, the effect of chromium, copper, nickel, and vanadium on the solubility of sulfur in solid iron was determined at 1000". The specimens for this investigation were prepared by melting electrolytic iron and reagent-grade alloying additions in an induction furnace under an argon atmosphere. The melts were allowed to solidify in

Jan 1, 1969

By C. H. Stewart, R. A. Fagin

A two-dimensional, three-phasereservoir simulator was programmed for a large memory digital computer. It was designed to provide a practical solution to describing the complex physical relation between the natural forces and the physical properties of a heterogeneous reservoir when subjected to a specific set of conditions. A reservoir study is briefly described to illustrate application of the model. A full volumetric account of three phases (oil, gas and water) is performed simultaneously throughout an integration net representing the reservoir. Absence of one or two of the phases is treated as a special case of the more general situation. Expansion (or contraction) of all phases, including rock expansion, is performed so that the pressure calculation is the general unsteady-state case. To account for the large variations of subsurface elevation encountered in some reseruoirs, and to allow for segregation of the various phases, a gravity head term is included in the basic drive potential. Appropriate fluid and rock properties are used in polynominal surface form (functions of pressure and/or depth) or they can be entered as space variables at each position of the integration net. An unsteady-state water influx calculation, based on the method of van Everdingen and Hurst, l was connected to the boundary of the matrix to simulate aquifers of various sizes. In addition to reservoir calculations, three-phase fluid flow from the producing depth to the wellhead, including provisions for gas lift, was incorporated in the simulator. A workover routine was also built which can automatically switch to a different set of production relations when a gas-oil ratio or water fraction reaches a limit; or it can shut-in the well if prescribed. INTRODUCTION This paper describes a reservoir engineering mathematical simulator used to represent the complex interaction of natural forces and physical properties of a reservoir during natural depletion or with various injection schemes. The simulator, which was programmed for a large memory digital computer, is a two-dimensional calculation which handles three mobile fluid phases simultaneously (oil, gas and water). Basic requisites for the method are individual well production and pressure data, hydrocarbon fluid properties, geological data (producing depth and net sand), capillary pressure data, relative permeability data and permeability and porosity information. Matching the past performance of a combination drive reservoir often has yielded information concerning continuity and the validity of basic data. Detailed predictions of future performance can be made for continuation of current depletion methods (natural depletion) as well as for various types of recovery by gas or water injection. Combination injection cases and pattern studies can also be performed. Workover programs, gas lift and different types of artificial lift programs have been investigated using a technique similar to that described by Kern and Nicholson2 except that conditions of pressure and saturation at the block within which the well is located are used rather than average reservoir conditions. Drilling additional wells to optimize profit was explored, both as to number and location, by placing wells at different spots within the reservoir matrix. Special depletion processes can be examined, such as upstructure drainage and lateral (or strike) waterfloods in thin oil columns. In one case the mathematics of the simulator were modified to calculate the displacement in the vertical plane rather than in the horizontal plane. In this manner specific reservoir problems can be studied, such as coning of gas and/or water around production points, fingering along permeable stringers or, more generally, frontal advances in a heterogeneous section.

Jan 1, 1967

By G. Bhat, J. F. Libsch

lsoembrittlement curves depicting the influence of time and temperature in the range 800' to 1260°F (425' to 680°C) on the development of embrittlement in a commercial chromium alloy steel and a commercial molybdenum alloy steel are presented. Two distinct regions of embrittlement occur in the chromium alloy steel: I—at 800' to 1000°F (425' to 540°C) and 2—in the region just below the lower critical temperature. Embrittlement is most pronounced at 800' to 1000°F, decreasing very rapidly with increasing temperature above this region, only to increase again as the lower critical temperature is approached. The data suggest two distinct modes of embrittlement with possible superposition of the two modes at extended embrittling times in the temperature range 1100° to 1150°F (590' to 620°C). While the molybdenum alloy steel shows little susceptibility to embrittlement at 800' to 1000°F (425' to 540°C), considerable embrittlement may occur just below the lower critical temperature. THE subject of temper embrittlement in alloy steels has received considerable attention in the last few years. Points of view on the mechanism of embrittlement differ, however, resulting in part from the incompleteness of the data developed and in part from the speculation regarding the susceptibility of plain carbon steel to temper embrittlement. Libsch, Powers, and Bhat1 carried out short-time embrittling treatments on an AISI 1050 steel and demonstrated that hardened plain carbon steels are quite susceptible to embrittlement when tempered in the range from 850°F (455°C) to the lower critical temperature. The isoembrittlement diagram,' representing the embrittling characteristics of this steel, is reproduced in Fig. 1. It is evident from the shape of the curves shown that embrittlement in plain carbon steel increases progressively with both temperature and time in the embrittling range. A comparison of the isoembrittlement diagram for AISI 1050 steel with that presented by Jaffe and Buffum' for an SAE 3140 steel shows that up to 930°F (500°C) the isoembrittlement characteristics of the plain carbon steel are similar to those of SAE 3140 steel, although the embrittlement is much more severe in the latter steel. Above 930°F (500°C), the rate of embrittlement in the plain carbon steel increases continuously with increasing temperature; whereas, in the SAE 3140 steel, the embrittlement rapidly decreases. The influence of alloying elements upon embrittlement during tempering thus appears to cause a decrease in embrittlement above the region of maximum embrittlement, i.e., 850" to 1000°F. The question naturally arises as to what effect individual alloying elements have upon the embrittling characteristics of the plain carbon steel. Current knowledge on the influence of alloying elements on temper brittleness may be found in the review papers of Hollomon" and Woodfine. Hollo-mon," from the results of other investigators, has shown that, in general, the amount of embrittlement increases with increasing alloy content (except for molybdenum and possibly tungsten and columbium). Jaffe and Buffum," by a comparison of the embrittlement in a plain carbon steel with that of a SAE 3140 steel postulated that the presence of alloying elements in moderate amounts tends to retard the development of temper brittleness. It is difficult to determine what effect chromium has upon temper brittleness, since most of the information available has been based on the combined effect of other elements with chromium, particularly nickel and manganese. However, Wilten, and recently Jolivet and Vidal,' Vida1, and Woodfine have reported that chromium steels are temper brittle, that the embrittlement is reversible with a maximum rate of embrittlement at approximately 975°F (525"C)," and that the susceptibility increases with increasing amounts of chromium. Taber, Thorlin, and Wallacel" have found a large embrittling effect with increasing chromium content in a medium C-Mn-Ni steel. But Hultgren and Chang," from their experiments conducted on synthetically prepared ternary Fe-C-Cr alloys, could not conclude that these alloys are susceptible to temper embrittlement. However, on addition of manganese or phosphorus, these Fe-C-Cr alloys became susceptible, from which fact they concluded that the embrittlement developed in chromium-bearing Fe-C alloys is due chiefly to the presence of these elements. Considerable data are available to show that molybdenum decreases the susceptibility of steel to temper embrittlement. However, its effectiveness in preventing or decreasing embrittlement appears limited to its presence in small amounts. Vidal" has shown that a plain 2 pct Mo steel was susceptible. Hultgren and Chang" also have shown that molybdenum additions in excess of 2 pct to synthetically prepared Ni-Cr steels did not prevent embrittlement. Jolivet and Vidal' and Lea and Arnold found that molybdenum reduced temper brittleness. Lea and Arnold further stated that molybdenum decreased the rate of embrittlement rather than the total amount of embrittlement, whereas Preece and Carter" have shown that the presence of molybdenum greatly reduces the equilibrium extent of the change at a given temperature but does not appear to influence the rate of embrittlement. There appears to be very little information as to how molybdenum by itself affects the temper brittleness susceptibility of a plain carbon steel.

Jan 1, 1956

By A. A. Venghiattis

This paper is discussed not because of its intrinsic value but because it has been related by its authors to the oilwell gun perforators. It is well known that conditions almost ever present in oilwell perforations are the overburden and the presence of the casing. Because of the lack of information in the paper on the dimensions or confinement of the target rocks, one is led to guess that they were not confined at all and, particularly, that no steel front plates were used on the impact face of the rocks to materialize the presence of the cemented casing. This situation, plus the fact that small steel balls have been used as projectiles instead of actual bullets, makes the whole thing unapplicable to oilwell perforation. When shooting is performed against target rocks confined (as shown on Fig. 1) in such a way as to give a fair image of the overburden applied to the formation to be perforated, as well as of the cemented casing, the following are found. 1. There is no cratering worthy of mention, even with bullets having 10 times higher impact energy per unit projected area than the steel balls mentioned in the article. This has been confirmed with sandstone as well as with other rocks (granite, limestone and chalk). See Figs. 2 and 3. 2. Penetrations vary closely as the logarithm of the impact velocity. On this matter I have established the relation

By C. L. Sollenberger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature's to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent.

Jan 6, 1958

By B. L. Averbach, M. Cohen, C. H. Shih

The isothermal formation of martensite is studied in Fe-Ni-Mn and Fe-Mn-C alloys under conditions where the athermal transformation is completely avoided, there being no martensite present at the beginning of the isothermal reaction. The initial rate of martensite formation is extremely low under these conditions, but it increases greatly as soon as some martensite is formed. It appears that true initial characteristics of the isothermal reaction can be studied only in samples wherein the formation of martensite on cooling is completely eliminated. THE phenomenon of isothermal martensite formation is well established1 -" but the observations have been made in the presence of varying quantities of athermal martensite. Complete avoidance of athermal martensite and the formation of martensite under pure isothermal conditions have been reported by Kurdjumov and Maksimova2 in an Fe-Ni-Mn alloy (23 pct Ni, 3.4 pct Mn, and the balance Fe) and have been confirmed by recent experiments of Cech and Hollomon in a similar alloy. In each case, the isothermal transformation rate was a maximum at the beginning of the transformation and decreased as the reaction proceeded. These initial transformation rates were used by Fisher7 for the confirmation of calculated nucleation rates based on classical nucleation theory extended to include the effect of elastic strain energy. Cech and Hollomon have admitted, however, that up to 3 pct martensite formed on cooling in their samples and thus was present at the initiation of their isothermal runs. In this paper, experiments on similar alloys are described, except that care was taken to remove the incidental martensite developed at the surface prior to the isothermal reaction. It is shown here that the reaction rate at the beginning of the strictly isothermal reaction is very low. As soon as some detectable amount of martensite is produced, the transformation rate increases rapidly but ultimately decreases as the reaction proceeds. When martensite is allowed to form isothermally in the presence of about 2 pct of prior martensite, the apparent initial reaction rate is a maximum and corresponds to the observations of Kurdjumov and Maksimova and Cech and Hollomon. It is evident that the cooperative nature of the martensitic reaction results in a significant stimulating or autocatalytic effect on the isothermal reaction rate. Experimental Procedure The chemical compositions of the alloys used in this investigation are listed in Table I. The Fe-Ni-Mn alloys A and B were melted in an induction furnace, cast into ingots 2 in. diam by 4 in. long, and forged into % in. diam rods. The manganese steel (alloy C) was melted in an arc furnace and cast into ceramic molds 1/4 in. diam by 5 in. long. The rods were sealed in evacuated Vycor tubes and homogenized at 1175" to 1200°C for 50 hr. The long homogenization resulted in some manganese loss from the surface, producing a thin layer of transformed material. This surface layer was removed by grinding and the specimens were then swaged to 0.050 in. diam wire. Measurements of electrical resistance were made with a Kelvin double bridge to follow the course of the martensitic transformation. A small permanent magnet was also useful in scanning an entire specimen for small localized quantities of martensite. This test is almost as sensitive as the electrical resistance method in detecting the presence of martensite (which is ferromagnetic in these alloys) and it was especially useful in deciding whether a specimen was completely free of martensite. The wire specimens (0.050 in. diam by 2.5 in. long) were sealed in evacuated tubes and austenitized for 5 min at 1150°C. The specimens were quenched into water and, unless otherwise stated, stress-relieved for 1 hr at 650 °C in order to induce greater uniformity in the subsequent martensitic transformation. As dem-

Jan 1, 1956

By T. F. Witheree

The Fletcherville Furnace was built in 1864 and 1865, making its first blast from August until October of the latter year, when it was blown out to prevent its " bunging-up." Repairs were made in time to enable it to be blown in again December 12th, 1865, the blast ending October 7th, 1866. Total product 1921.15 tons iron, an average of 6.8.2.5 tons per day, from ores yielding 44.8 per cent. Consumption of charcoal 223.2 bushels per ton of iron. The furnace journal up to this time shows no record of furnace dimensions, or temperature of the blast, but as near as can be ascertained, they were as follows, viz.: Height of stack, 42 feet. Diameter of bosh, 11 feet. Angle of bosh, 71/2 inches to 12 inches rise, about 58°. Diameter of open tunnel head, 42 inches. Number of tuyeres 3 ; each 3 inches in diameter. Dam 15 inches high. Tuyeres 24 inches high. Tymp 224 inches high. Diameter of steam cylinder, 20) inches. } Diameter of blast cylinder, 64 inches. } Stroke 5 feet. The engine is direct-acting horizontal non-condensing. December 26th, 1866, the furnace was again put in blast, having been considerably altered in the crucible; the height of stack, bosh, and tunnel head remaining as before. Six tuyeres were put in, three in each of the side arches. The hearth or crucible was rectangular in form, 3 feet wide x 31/2 feet long x 64 feet high. Inclination of bosh 58°. Height of tuyeres 26 inches; nozzles 21/4 inches diameter. Temperature of blast estimated to be about 500°.

By R. R. Vandervoort

The creep behavior of Nb(Cb), Ta, Mo, and W was determined under conditions of constant atomic dif-fzisivity, constant stress to elastic modulus ratio, and nearly equivalent grain size, and the steady-state creep rates obtained from these tests were correlated with calculated stacking fault energies for the metals. These results, in conjunction with similar data for several fccMetals,13 suggest that stacking fault energy may influence the creep strength ofbcc metals. The interrelationship between steady-state creep rate, subgrain size, and stacking fault energy was examined. It was found that the subgrain size for a given creep stress, increased as stacking fault energy increased, but that this relationship did not cormpletely account for the effect of stacking fault energy on creep rate. The crystallography and energetics of stacking fault formation in bcc metals has been discussed by a num-ber of authors,1-5 and impurity stabilized stacking faults on (112) planes have been observed in Nb,6,7 w,8,9 Fe,] and V" by transmission electron microscopy. However, a crucial question is whether or not stack-ing faults influence the mechanical strength of bcc metals. Potentially, stacking faults could increase strength by reducing the mobility of the partial dis-locations bounding the fault, by acting as barriers to slip dislocations, and by retarding the climb of dislo-cations during high-temperature deformation. The objective of this study was to seek a correlation be-tween creep strength and stacking fault energy for several bcc metals; namely, Nb, Ta, Mo, and W. The creep behavior of most polycrystalline metals and alloys at high temperatures and moderate stresses can be described by the following relation:11,12 im=Af(s) where i, = minimum creep rate, A = constant, j(s) = a function involving metallurgical structure, a = applied stress, E = average elastic modulus at the test tempera-ture, w = constant (equal to 5 for most pure metals), D = diffusion coefficient. One factor in the structure function F(s) which sig- R. R. VANDERVOORT, Member AlME is Research Metallurgist, Process and Materials Development Division, Chemistry Department, Lawrence Radiation Laboratory, University of California, Livermore, Calif. Manuscript submitted February 28, 1969. IMD nificantly affects the creep resistance of fcc metals is stacking fault energy, and creep rate has been shown to vary directly with stacking fault energy to the 3.5 power." In the latter investigation, four fcc metals of widely different stacking fault energies (Ag, Cu, Ni, and Al) were creep tested at a constant stress to modulus ratio of 1.21 x 10-4, at a constant diffusivity of 2.7 x 10-12 sq cm per sec, and at nearly equivalent grain sizes of about 0.7 mm. The creep data were then correlated with stacking fault energies. In the present study, a similar procedure was followed. All materials used in this work were consolidated by powder metallurgy techniques. Impurity contents in the as-received materials are listed in Table I. Chemical analyses showed that no measurable contamination of the test specimens occurred during pretest annealing treatments or creep testing. Specimens with a gage section 0.75 by 0.125 by 0.050 in. were creep tested in tension in a vacuum of less than 10-9 torr. Deformation at temperature was measured by tracking fiducial marks on the gage section of the specimen with an optical comparator. Optical deformation measurements also permitted observation of the macroscopic characteristics of the deformation Table I. Typical Specimen Impurity Content, ppm Nb Ta Mo W C 45 10 155 6 O 185 30 4 10 N 30 6 3 2 H 5 I 1 <1 als 3 10 2 15 Ca <5 I3 5 Cr 5 <3 10 <5 Cu 10 50 2 15 Fc 10 10 150 35 Ni 2 150 20 <5 Si <I0 1 3 <10 Ta 100 Ti 10 8 1 Zi 15 50 1 3 Table II. Test Conditions for Constant Stress-Modulus Ratio of 6 X 10.&apos; and Constant Diffusivity of 2.7 X 10-12 sq cm per see, and Grain Size Values for the Given Pretest Annealing Treatments Literature references Pretest Annealing for E and D Treatment Stress, Temperature, ___"&apos;Values__ Grain Tempera-Metal psi "C E D Size, mm ture, .C Time hr Nb 745 1525 14 15 to 17 0.83 1650 I Ta 1220 1770 18 19.20 O.91 1800 I Mo 1975 1630 18 21 0.77 2200 I W 2140 2265 18 22 040 2400 5

Jan 1, 1970

By Sheldon Rideout, E. L. Kamen, B. S. Lement, Paul A. Beck, W. D. Manly

The 1200°C isothermal sections of the following ternary phase diagrams were investigated: Cr-Co-Nil Cr-Co-Fe, Cr-Co-Mot and Cr-Ni-Mo. In all these systems the u phase was found to form extended solid solutions. Two new ternary phases of unknown structure were identified. The existence range of intermediate phases of transition elements was correlated with 3d electron vacancy concentrations. THE occurrence of extensive ternary d solid solutions in the Cr-Co-Ni and in the Cr-Co-Fe systems was described in a brief note.&apos; More recently d- solid solutions were also found in the Cr-Fe-Mo system by two independent groups of investigators.2,3 The existence of binary d phases in the V-Co and V-Ni systems, predicted in ref. 1, was experimentally discovered recently by Duwez and Baen and independently by W. B. Pearson, J. W. Christian, and W. Hume-Rothery.5 Duwez and Baen stated two general conditions for the occurrence of the d phase in alloys of the transition elements: "(1) The atomic diameters of the two metals do not differ by more than 8 per cent. (2) One of the two metals has a body-centered cubic structure while the other is face-centered cubic, at least in one of its allotropic forms." In the course of an extensive research program conducted at this Laboratory under the sponsorship of the NACA, several ternary systems, containing d solid solutions and also certain new ternary phases, were investigated. The present report describes the investigated portions of the 1200°C isothermal sections of the following ternary phase diagrams: Cr- Co-Ni, Cr-Co-Fe, Cr-Co-Mo, and Cr-Ni-Mo. It was found that the range of existence of the d phase in these four ternary systems, as well as in one of two ternary systems which were investigated by others, can be fairly consistently described in terms of electron vacancy concentrations. This supports the suggestion of Sully and Heal" that the d phase is an electron compound. Experimental Procedure The ternary alloys were prepared by vacuum induction melting in zirconia and alumina crucibles. Lot analyses of the metals used are given in Table I. Specimens of all alloys were annealed at 1200°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. Alloys consisting mainly of

Jan 1, 1952