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By George A. Roberts

The development of an alloy system, high-speed steel, is used as an example of the progress of physical metallurgy. Tracing the history of men and their thoughts as they studied and invented and modified these materials, the story of high-speed steel since the 1890's is seen to be a long, slow, but steady progression of achievements. Today's multiplicity of high-speed steels are the result. Data are presented on quantitative metallography of carbides in high-speed steel with high vanadium content using the QTM instrument. Grindability as well as mechanical properties are related to the content of excess MC and M6C carbides in a series of high-speed steels and the newer matrix steels. These emphasize the present state of knowledge and show the current stages of thought that may affect the development in succeeding years. It is a great thrill for me, an ex-research metallurgist and ex-practicing metallurgical engineer, to speak to an audience currently engaged in both pursuits on the occasion of the 43rd Howe Memorial Lecture before the Iron and Steel Division of the AIME. I shall not review Henry Marion Howe's distinguished career, so adequately reviewed in Maxwell Gensamer's contribution in the 1965 AIME History of Metallurgy, except to point out that, while leading the life of an intellectual, he worked as a practicing research metallurgist and a practicing metallurgical engineer for significant periods of time and contributed greatly in both areas. For those of you who believe, as I do, that in the intellectual activity of metallurgy we are blessed with an intimate mixture of science and engineering (see Mehl's 1960 Howe Lecture), we might recall that Howe, while pursuing a life of writing and teaching in later years, served as the first Chairman of the Division of Engineering of the National Academy of Sciences. That metallurgists were called upon then to lead an engineering recognition movement is perhaps related to the strong part played by the AIME and its members in the recent establishment of a National Academy of Engineering and to the fact that a metallurgist is its head, 47 years after Howe served. I stress these engineering aspects for I wish to talk about a metallurgical engineering subject today. Alloy systems, physical metallurgy, and steel blended with an historical perspective and a report on new techniques to improve the old will, I trust, be of sufficient interest to bring these lectures back to the physical-metallurgy banner from which they have departed for 4 years. Those process metallurgists, open-hearth fiends, and physical chemists among you will just have to be patient. The development of an alloy system is the engineering application of scientific thought and fact. There are many interesting alloy systems, developed to a high degree of technology and sophistication over the past 40 to 70 years. These systems are bound together and related by a similar set of characteristics. For example, stainless steels are a system in which the members are related by a high chromium content which gives a corrosion-resistant characteristic. A subfamily in this system would be austenitic steels

Jan 1, 1967

By A. J. de Witte

It has been observed that upon invasion of a sand containing oil or gas and connate water by mud filtrate the hydrocarbons are more rapidly flushed by the filtrate than is the connate water.' In time, it appears that the following displacement pattern emerges: oil (or gas) is being swept ahead by connate water which, in turn, is pushed by invading fluid. Eventually the connate water may have "banked up" sufficiently to form a zone of appreciable thickness leading the invading front. In the extreme case, Fig. 1 shows how the situation will develop.' Immediately adjacent to the borehole (radius r) there is a zone, the invaded zone proper, where the connate water has been flushed out completely and which contains only residual oil or gas and mud filtrate. This zone (extending out to a radius ri) grades more or less abruptly into the next (thickness A), which contains only residual hydrocarbon and connate water. Beyond it, again more or less sharply bounded, extends the virgin formation with the original interstitial water saturation Sw. The various saturations are indicated in Fig. 1. The three zones generally will be marked by resistivity contrasts owing to their different fluid contents. As the connate water is usually more saline than the invading fluid, the second zone having a high connate water saturation forms a concentric cylindrical ring or annulus of low resistivity R, around the borehole.',' It will be referred to as the "low zone." Fig. 1 shows schematically the resistivity profile. It is clear that the phenomenon of a low zone could not occur in invaded water sands. The presence of a low zone, therefore, would be a qualitative indication of a hydrocarbon-bearing formation. Granted that the phenomenon is real, if it were pronounced enough to be detected, one might thereby have a means of locating oil or gas in the ground. This is the aim of the "displacement logging" method.' In any case, the presence of a low resistivity zone will affect the reading of electric logs. Using conventional log interpretation techniques, one must be aware of this and, if necessary, correct for it. Whether correction or detection should be the goal will depend primarily on the magnitude of the effect. The type of log which is likely to be affected most is the induction log. The current pattern of an induction log is concentric with the borehole. Any concentric ring of low resistivity, therefore, will tend to become crowded by current lines. This zone of maximum current density will obscure the relative contributions to the current conduction by other portions of a bed making, for instance, the contribution of the virgin formation less significant and thus detracting from the value or the induction log as an R, reading device. The present note is intended to ascertain the maximum possible effect of a low zone in the extreme case portrayed by Fig. 1 on three commercially available types of induction logs, sc., 5 FF 27, 5 FF 40 and 3 F 60. Type 5 FF 27 or 5 PF 40 is currently run in conjunction with a 16 in. normal and SP log. This combination is gradually replacing the regular electric survey (two normals and one lateral) as a standard log in many areas. On the basis of the scheme of Fig. 1 (sharp boundaries between successive zones), the thickness of the low zone may be computed for various amounts of infiltration measured by the ratio of invaded zone diameter to hole diameter D,/d. Referring to Fig. 1, we can set up a material balance for the water displaced from the invaded zone proper and the water present in the low zone. The volume of connate water displaced from invaded zone upon flushing by mud filtrate is: V1 = e p (r2 - r2) ? Sw . where c = bed thickness ? = porosity Su, = original connate water satu-ration. The volume of water finally accu-mulated in the low zone is: Vz = e p [(r1 -?)2 - r2 4] ? Sw . where SW1 = 1 — Sor = "water" saturation in the invaded and low zones both. The volume of water originally present in the low zone is:

Jan 1, 1958

By Claude P. Heiner, Carl S. Westerberg

OBSERVATION of the clinkering action of coal from the Castle Gate D seam in underfeed stokers over a period of years has given rise to the present investigation of the effect of bony coal on clinkering. Some very costly examples of slagging clinkers in particular cases have been of especial interest to the authors. In such cases coal analyses and ash-softening and fluid temperatures have been found of little value. In general, it was noted that slagging was accompanied by a somewhat higher ash content of the stoker slack, and the suspicion naturally arose that foreign matter was the troublemaker. One would naturally suspect bony coal and rock impurities because of their occurrence and prevalence within the seam and the relative absence of sulphur or other impurities in the coal mined. The test results given herein indicate that the concentration of the bony coal and rock impurities in the coal determines the clinkering tendencies of the ash during combustion. CASTLE GATE D SEAM Extending from the Utah-Colorado line near Grand Junction, Colo., westward to Greenriver, Utah and thence in semi-circular form north and westward to Castle Gate, and from there southward to Mt. Hilgard in central Utah, is a line of nearly perpendicular cliffs, composed of interbedded massive sandstone and shales, making up the coal-bearing horizon of the Mesaverde formation of Upper Cretaceous age. The cliffs face roughly concentrically toward the south and southeast and the strata, with conformably enclosed coal beds, gently dip away from the face of the cliffs and at right angles to their front line. Back of these cliffs the mountain masses rise to an altitude of from 8000 to 10,000 ft. above sea level. Stretching away from their foot is a great shale plain, on which the towns are situated and over which the railroad lines and highways run. The Castle Gate mines enter the coal beds at their outcrop; the workings extending within a particular coal bed away from the outcrop and under the mountain mass back from the cliff line (Fig. 1). Throughout the Mesaverde formation in the Castle Gate general area, there are from two to five workable coal beds. Usually not all of these are coincidentally of workable size and merchantable quality throughout any given large tract. In the Castle Gate mine area, the base of the Mesaverde horizon and coal measures is marked by a massive, cliffmaking, gray sandstone bed 6o to 8o ft. thick. Locally this is referred to as the "Castle Gate sandstone floor." Frank R. Clark, in U. S. Geol. Survey Bull. 793, designates it as the "Aberdeen sandstone." At Castle Gate the various coal beds are designated by the letters A, B, C, etc., commencing with the lowest bed. Fig. 2 is a graphic generalized vertical section, compiled from physical exposures

Jan 1, 1941

By A. G. Paithankar, G. B. Misra

Although certain physical mechanical properties of rocks have been claimed to give an estimate of penetration rate in percussive drilling, the authors' work shows that the correlation of penetration rate with individual rock properties is Poor. The authors have developed a good correlation between penetration rate and a set of rock properties but the relation is complex. Energy per unit volume has been used as a measure of penetration rate in percussive drilling by Hustrulid and Fairhurst; however, their test setup is large wing a full size drill bit. The authors determined the minimum energy for unit volume Ev min for any rock at the optimum index angle in a simple laboratory drop tester wing a sharp microbit with a tip angle of ll0°. This Ev min has been found to correlate well with penetration rate obtained in controlled laboratory drilling in different rocks for different stages of bit wear. A comprehensive relation has been developed between penetration rate and Ev min.

Jan 1, 1981

By D. N. Witman

One of the special uses to which the electric furnace has been put recently is the melting of an alloy of nickel and cast iron for the production of electrical-resistance grids. The metal sections of these grids, Fig. 1, are quite uniform for each pattern, but there is, among the various patterns, a variety of thicknesses. The cross-sections vary from 1/2 by 3/16 in. to as small as 1/8 by 1/8 in. The electrical resistance of a perfect casting lies within 10 per cent. above or below the fixed listed resistance for each pattern. Good molding is essential to success in the making of these grids, for with absolutely correct metal, a variation of 0.01 in. in width and thickness of section on some of the patterns may mean as much as 12 or 14 per cent. variation in resistance. The service for which these castings are intended demands that the metal, even in the smallest castings, be very soft, showing an open, gray, highly graphitic structure, in order that they may be resistant to shock, and stand up well under rough usage. The metal used for this purpose is a gray iron alloyed with 4 to 5 per cent. of nickel, which element, when the composition of the alloy is correct, imparts toughness and pliability to the metal and helps to overcome the tendency of metal to run white and become brittle because of the rapid cooling action of the sand mold. When cold, these castings can be twisted into various shapes, taking a permanent set without breaking. The alloy has approximately double the e1etrical resistance of ordinary cast iron. The metal specification is as follows: Per Cent. Silicon............................................. 2.40 to 2.60 Sulfur............................................. Under 0.05 Phosphorus......................................... Under 0.08 Manganese......................................... Under 0.40 Total carbon....................................... 3.60 to 4.00 Nickel............................................. 4.00 to 5.00 Copper............................................ 0.50 to 0.70

Jan 1, 1922

By D. N. Witman

One of the special uses to which the electric furnace has been put recently is the melting of an alloy of nickel and cast iron for the production of electrical-resistance grids. The metal sections of these grids, Fig. 1, are quite uniform for each pattern, but there is, among the various patterns, a variety of thicknesses. The cross-sections vary from 1/2 by 3/16 in. to as small as 1/8 by 1/8 in. The electrical resistance of a perfect casting lies within 10 per cent. above or below the fixed listed resistance for each pattern. Good molding is essential to success in the making of these grids, for with absolutely correct metal, a variation of 0.01 in. in width and thickness of section on some of the patterns may mean as much as 12 or 14 per cent. variation in resistance. The service for which these castings are intended demands that the metal, even in the smallest castings, be very soft, showing an open, gray, highly graphitic structure, in order that they may be resistant to shock, and stand up well under rough usage. The metal used for this purpose is a gray iron alloyed with 4 to 5 per cent. of nickel, which element, when the composition of the alloy is correct, imparts toughness and pliability to the metal and helps to overcome the tendency of metal to run white and become brittle because of the rapid cooling action of the sand mold. When cold, these castings can be twisted into various shapes, taking a permanent set without breaking. The alloy has approximately double the e1etrical resistance of ordinary cast iron. The metal specification is as follows: Per Cent. Silicon............................................. 2.40 to 2.60 Sulfur............................................. Under 0.05 Phosphorus......................................... Under 0.08 Manganese......................................... Under 0.40 Total carbon....................................... 3.60 to 4.00 Nickel............................................. 4.00 to 5.00 Copper............................................ 0.50 to 0.70

Jan 1, 1922

By Arthur Phillips, Carl H. Samans

The study of anisotropy in metals has been greatly stimulated in recent years by the rapid development of X-ray methods for determining the crystallographic relationships of wrought and annealed materials. Prior to this time the knowledge regarding the directional properties of commercial alloys consisted almost exclusively of observations of a practical nature made during the fabrication of metal objects, supplemented by a limited number of mechanical tests on specimens cut at various angles to the direction of working. Such observations clearly indicate that the common methods of cold-working metals cause both a crystallographic and a mechanical fibering varying in character and degree according to the nature and extent of the deforming process. Even after annealing, following certain not too well known combinations of reductions and anneals, a preferred orientation may exist,, thereby constituting a residual fiber effect sufficiently pronounced to manifest directional properties. With the application of the X-ray the experimental horizon was extended chiefly because the study of anisotropic metals promised to offer direct and quantitative evidence regarding the involved mechanism of fragmentation and plastic flow. As a natural consequence the intensive studies in this direction have yielded a vast accumulation of data of ultimate potential value. Unfortunately, however, as is commonly the case in entering a virgin field of experimentation, many of the data cannot be molded into complete and coherent form because of the many unrelated conditions of the experimental projects. Again, the results of the study of single crystals have been rather naturally but at times indiscriminately applied to poly crystalline metals. Furthermore, sweeping statements have been made regarding the behavior during working and annealing of metals and alloys, entirely on the basis of similarity in lattice arrangement. There is abundant reason for believing that relatively small concentration variables, differences in magnitude and distribution of applied stresses, and the character of associated annealing treatments may in some cases greatly influence the mechanics of flow

Jan 1, 1933

By Richard Downs, Stephen P. Burke

The oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combustion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the conditions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 2H2O + 7O2 ? 2FeSO4 + 2H2SO4 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to disclose any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1938

By Richard Downs, Stephen P. Burke

The oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combustion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the conditions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 2H2O + 7O2 ? 2FeSO4 + 2H2SO4 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to disclose any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1938

By C. W. Nicolson

THE Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less. Practically all of the leases granted in the past required the erection of a concentrating plant on each lease, a condition that has had a pronounced effect upon the mining and milling methods of the district, since the apparent ore reserves on each tract were too small to justify large

Jan 1, 1938

By J. M. Gaines, C. H. Herty

IRon oxide (FeO) plays an extremely important part in the manufacture of steel. In the open-hearth furnace and the Bessemer converter it is the chemically predominant compound and controls to a large extent both the operation of the furnaces and the composition and quality of their products. Almost all of the refining action is carried out through the medium of FeO, which oxidizes carbon, manganese, silicon and phosphorus. At the end of any open-hearth or Bessemer heat the steel contains dissolved iron oxide, which must be wholly or partly eliminated. The type of deoxidation product depends on the amount of dissolved iron oxide and on the deoxidizer used. After the heat has been deoxidized and while it is being teemed, iron oxide diffuses from the ladle slag into the metal, causing losses of deoxidizer and increase in iron oxide content of the steel. It is generally believed that non-metallic inclusions are responsible for a great many failures of steel in service and for decreased yield of steel during rolling. The basis of most non-metallic inclusions is dissolved iron oxide. This investigation was undertaken in order to determine the amount of iron oxide that will dissolve in iron under various conditions. Steel-making slags are complex and it has been thought best to determine solubility under simple slags as a first step. The study is being continued under slags whose compositions approach those of operating slags Previous Investigations The solubility of oxygen in iron has been determined by a number of investigators (see Table 1) but their effort's have been directed toward the

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,' and

Jan 1, 1962

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active'.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of' gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

By E. F. Ketterer, D. B. Collyer, A. B. Wilder

The microstructural stability of 59 carbon and low alloy steels after 34,000 hr exposure at 900' and 1050°F, including the weld heat-affected zone, is discussed. The tensile and creep rupture properties of the parent metal of many of the steels before and after 10,000 hr exposure are presented. SEAMLESS pipe has been used for many years at elevated temperatures. When seamless first began to be used, operating temperatures and pressures were relatively low and the steel produced adequately met the existing requirements. The need for knowledge of creep properties and graphitiza-tion was nonexistent. Today the requirements for tubular products have changed considerably. Operating temperatures and pressures are increasing continually and corrosion, particularly at high temperatures, presents a problem. Carbon steels have, under these conditions, certain economic advantages particularly in oil refinery use. However, the use of low alloy steels in the generation of steam power has increased appreciably due to the influence of molybdenum on creep strength and the control of graphitization with chromium. The behavior of carbon and certain low alloy steels after long periods of exposure at 900° and 1050°F (480° and 565°C) has been investigated. The steels were examined before and after 10,000 to 34,000 hr exposure. Results obtained with material exposed at 1200°F (650°C) are not presented due to the severe oxidation and resulting decarburiza-tion after long periods of exposure. The graphitization characteristics of carbon and low alloy steels are of fundamental concern to the users of these materials. This is particularly true where welded joints are employed. In order to evaluate properly the behavior of steels at elevated temperatures, it is desirable to employ not only long periods of exposure under controlled conditions, but to use material with known properties and steelmaking practices. The purpose of this investigation has been to study the microstructure of the weld and the tensile and creep rupture properties of the parent metal after long periods of exposure at elevated temperatures. In the report'.' of a previous investigation data were presented on the microstructure, impact strength, hardness, and oxidation characteristics after 10,000 hr exposure at elevated temperatures. When this investigation was planned, methods for controlling the graphitization characteristics of steel were not established and, therefore, a number of special alloy steels were included in the study. During the exposure of these steels, the influence of aluminum in accelerating the rate of graphitization and the inhibiting power of chromium were established by various investigators. Also, the vanadium-bearing steels, because of their outstanding creep properties, received attention. As a result of these developments, considerable progress has been made in the field of high temperature tubular products, and the necessity for special alloys to prevent graph-itization has been restricted largely to the use of chromium. Material Chemical analysis, deoxidation treatment, and austenitic grain size of the 59 steels discussed in this paper are shown in Table I. The steels were forged to 1x1 in. bars with the exception of steels 12B, 12DX, 12DY, 12DZ, 70, 70A, 72 to 78, 82, and 83 which were machined from heavy wall pipe. All bars were surface ground before exposure. Heat treatment before exposure is shown in Table 11. The majority of the steels included were melted in either a basic open hearth or basic electric furnace; how-

Jan 1, 1955

By S. R. B. Cooke, C. E. Thurston, G. Kudo

The trend toward utilization of low grade iron ores means that more efficient methods must be developed for their concentration. The collecting ability of fatty acids derived from fish oils has been extensively investigated by Cooke.' Tuna oil, a byproduct of the tuna canning industry, is one of the lower priced fish oils. Utilization of tuna oil fatty acids as collectors in the flotation of iron ore might be economically feasible under certain market conditions, especially if their efficiency were high. Crude or unfractionated tuna oil fatty acids, and five fractions derived therefrom, were tested for their ability to concentrate a commercial specularite ore from northern Michigan. A commercial fatty acid derived from tall oil, and commonly used in nonsulfide flotation, was used as a reference. The crude fatty acids were obtained by simple saponification of tuna oil. Fractions A and B were obtained by acetone precipitation of the crude acids at -5O and -2S°C, respectively. Fraction C was obtained by a partial fractional distillation at 12S°C and at a pressure of 3y in a centrifugal molecular still in order to remove the shortest and longest chain fatty acids of tuna oil as well as oxidation products present in the original mixture. Fractions D and E were prepared by a chilling process in order to precipitate the unwanted saturated fatty acids. Yields and iodine values of the materials used are listed below: The seven samples were used as collectors in a laboratory procedure patterned after the commercial process for flotation of Michigan specularite ore. The outline of the procedure is that previously described1

Jan 1, 1962

By L. F. Mondolfo, B. E. Sundquist

The crystallographic orientation relationships resulting when lead is nucleated from the liquid by Ni, Cu, Ag, and Ge were determined. For each nucleating agent several definite orientatioz relationships were found. These relationships seemed to be controlled by good symmetry relations and low crystallographic disregistry between mating planes. For any given nucleating agent the under colling for nucleation was found fairly constant and independent of the orientation relationship and consequent disregistry. It was also found that, upon re melting and refreezing the Pb, the orientation relationship was changed. These findings prove that crystallographic disregistry is not the controlling factor in heterogeneous nucleation from the liquid. The results of this investigation tend to confirm the theory presented in a preceding paper that heterogeneous nucleation starts with the formation of an adsorbed layer of nucleated metal on the nucleat-ing impurity. Evidence is given that cavities in the nucleating agent act as centers of nucleation. IT has long been known' that solid extraneous particles are active in catalyzing phase transformations that occur in a system, particularly condensation and crystallization. It is well established that these heterogeneities act as catalysts by providing surfaces upon which nuclei of the precipitating phase can form with activation energies smaller than those required for homogeneous nucleation. Numerous investigations have shown that in this process of heterogeneous nucleation: a) the nucleus forms with one, or several, definite crystallographic orientation relationships with the nucleating phase2-4 and b) that there is a small range of undercoolings or super saturations characteristic of the nucleation of a given solid on a given Substrate.5-10 Turnbull and vonnegut11 have developed a theory based on theories developed by Volmer12 and Turn-bull and Fisher1= for heterogeneous nucleation from gases and liquids, that relates the super saturation or undercooling required for nucleation to the dis-registry between the lattices of the nucleus and the nucleating agent. This theory predicts that nucleation should occur with the orientation relationship between the nucleus and nucleating agent that minimizes the disregistry. Further, it predicts that the undercooling or super saturation necessary for nucleation should be a function of the disregistry. Numerous investigations have dealt with the orientation relationships resulting from the condensation of vapors onto crystalline solid substrates2,3 and a few with the nucleation of one phase by a second phase in solidification4,14. Others have dealt with the supersaturation8-10 and undercooling5-7 associated with nucleation in condensation and solidification respectively. However, there is virtually no report that gives both of these factors for the same system. In this investigation a study was made of the undercoolings and orientation relationships resulting when Pb is nucleated from the liquid by Ni, Cu, Ag, and Ge. It was the purpose of this investigation to check the Turnbull-Vonnegut theory, i.e., the importance of crystallographic disregistry between nucleating catalyst and nucleated metal. The results indicate that disregistry is not an important factor in nucleation and that the nucleation process is probably somewhat more complex than current theories suggest. EXPERMENTAL PROCEDURE Small single crystals of nickel, copper, silver, and germanium were prepared from materials of four to five nines purity, and the Pb used was also 99.999+ pet pure. Cu and Ag single crystals were prepared by sealing small chips of Cu or Ag in an evacuated quartz capsule and heating the capsule at 2000°F for 1 hr before cooling. Nickel crystals of 200 diam were also prepared in evacuated quartz capsules, but melting was done by heating the capsules in an oxy-acetylene flame for a few minutes. These spheres were invariably polycrystalline so

Jan 1, 1962

By George D. Roberts

Civil engineers are primarily interested in maximum core recovery. This is even more important in foundation work than in mining investigations where sludge samples are of some value. The soft materials, such as clay, gouge, or partially decomposed seams that are most readily ground up or washed away, are the materials that usually have the greatest influence on foundation and leakage conditions. Undisturbed samples of such materials should be obtained for detailed geological examination and laboratory tests. Therefore the attainable goal of sampling in connection with foundation investigations is the recovery of 99.9 pot of undisturbed core. Factors Causing Core Losses The principal factors contributing to core losses are: (1) coring badly fractured or very soft material; (2) Use of improperly designed coring equipment, including the use of bits of too small a diameter; (3) lack of the proper training and attitude on the part of the drillers and pertinent technical information on the part of the supervising personnel. Little can be done about the character of the material being cored but the other two factors contributing to unsatisfactory performance can be corrected. Although the title of this Paper is the improvement and standardization of core barrels, it is believed that the drillers' shortcomings and the lack of pertinent technical literature are more detrimental to good core recovery than either of the other factors. Uses For Large Diameter Core Barrels It is well known that the use of larger diameter bits and core barrels generally produce better cores, particularly when sampling soft or broken material. The use of larger and larger bit diameters and the insistence on better core recovery is well demonstrated by the change in practices of the various districts of the Corps of Engineers. Today NX core is the smallest diameter commonly permitted for investi-gational work and the more active districts are using coring bits up to 6 in. in diameter, as well as 36 and 40-in. calyx rigs. The latter size has proved to be just as economical because it provides more room for ctured removal and cleanup operations. The use of large diameter cores to replace the driving and jacking methods of obtaining soil samples is also increasing. The 57/8-in. Denison sampler, developed by H. L. Johnson to obtain samples from soft formations, is one example. The principal uses for bits larger than NX are: sampling soils and semi-consolidated rock; sampling decomposed rock or rock with soft seams; sampling concrete; obtaining samples for laboratory tests; drilling drainage holes, and other miscellaneous work. Core Drilling Practices of Several Engineer Districts Little Rock District The writer was employed in the Little Rock District from 1938 until 1942. Prior

Jan 1, 1949

By S. Zelouf, G. Simkovich

THE role that impurities play as dopants in the movement of species in ionic and semiconductor crystals was first conclusively demonstrated by Koch and Wagner.' At a later date Wagner demonstrated the effect of small amounts of alloying additions upon oxidation rates of pure metals, i.e., the effect of impurities as dopants in the scale being formed.'

Jan 1, 1970

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."' These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11'74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By F. M. Simonds, E. Z. Burns

The Rawley property is located in the Kerber Creek mining-district, Saguache county, Colorado, at an elevation of 10,600 ft. (See sketch-map, Fig. 1.) Ore was found in this vicinity as early as 1880, and claims covering a large area were located and in many instances patented. The ores, however, being of comparatively low grade, and the nearest railway station, Villa Grove, being some 20 miles away, it is extremely doubtful whether any considerable amount of ore was ever handled at a profit. It is safe to say that several hundred thousand dollars were spent (a large part in building mills) previous to 1902-03. About that time a very capable promoter gathered together a group of these claims and interested some New York people, who had had no previous mining experience, in the purchase of these claims. Following the organization of a company, this promoter became General Manager. As often happens under such conditions, the first step was to erect a mill to treat 100 tons per day. It may not be fair to this enterprise to say that the failure which followed might have been foretold, simply on general principles, but this much is certain—the water supply fluctuates in the course of a season through a wide range and for a considerable portion of the year was inadequate to run this mill at capacity. Further, it is currently reported that some of the mill foundations were placed on ice. However true this statement may be, it is a fact that, when first inspected by us, many of the belts in the mill were held on'their pulleys by means of idlers. A shut-down followed, with a material re-adjustment of interests, at which time we became consulting engineers for the company.

Jan 1, 1914