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By Dwight K. Smith, Greg Carter

Studies have been conducted on The properties of many deep well cementing compositions to determine their Strength behavior over curing periods to 180 days at elevated tem-peratures and 3,000 psi pressure. This pressure results in essentially the .vat, compressive strength as that obtained with much higher pressures in ac-cordance with the findings of an API subcommittee ' These different compositions include API C1asses A, E, and F cements containig additives such as retarders, berrtorlite, heavy weight materials and pozzolans. All compositions except mixtures of Poz-zolrrrts and hydrated lime show from mild to severe degrees of strength lass over a temperature rang from -730 to 320" F after setting. Pozzolatl-time compositions actually gain in strength with time at these high temperatures. Other chemical find physical properties evaluated to observe their inter-relation.ship with Strength loss show very little correlation except in per-meability. As retrogression in strength increases, the permeability of set cement increases. X-ray difraction patterns on the set products indicate the formation of certain compounds having little or no strength value in those cementing compositions where strength loss was more severe. INTRODUCTION As a result of the growing trend toward deep well completions, a study has been made on the properties of the various cementing slurries presently in use at elevated temperatures and pressure. The strength of these compositions is of prime importance in selecting the most suitable material for use at high temperatures, to determine WOC time and the proper time to perforate with a minimum of shattering. Of primary interest in this investigation was the strength behavior of various compositions currently in use, and the effect of additives on cement after long periods of curing under severe conditions. Earlier investigators have pointed out that the strength of some cements will increase with increasing curing temperature to about 220 to 340" F, but at higher temperatures a loss in strength occurs at extended time intervals. Studies by the API Mid-Continent District Study Committee on Oil Well Cements' outlined a testing procedure whereby field conditions of temperature and pressure could be simulated in the laboratory.' It was observed that retarded cements undergo changes at elevated temperatures and some lose as much as 50 per cent of their early strength when cured at high temperatures. The scope of these tests was limited to curing periods of 1 to 28 days; additives were not covered in this study. Saunders and Walker' found that the use of additives influenced the strength behavior of cements at high temperatures, but studies were conducted only to a seven-day curing period. Ludwig and Pence' conducted an investigation of two types of cements under elevated pressures and temperatures in an effort to explain the causes of this loss in strength phenomenon. It was observed that with retrogression in strength there were other physical and chemical changes which took place as the cement aged. Today there are a number of cementing compositions available for use at well depths below 10,000 ft. Since all these earlier investigations were limited in curing time as well as the number and type of compositions studied, it was believed that a more extensive study should be conducted on the properties of cements at elevated temperatures, and this work should include those compositions actually in general field use at this time.

By G. S. Cole, G. F. Bolling

ThE exact type of fluid flow which occurs in a solidifying ingot is important in determining subsequent grain structure. This has been shown in studies of natural Convection" and of forced stirring or other disturbances of the melt."16 We shall explicitly argue that a complement to the existing natural flow in an ingot should be more effective than other types of flow in promoting the columnar-to-equiaxed transition. The ultimate effects of fluid flow upon structure is one of the topics of solidification that we have investigated in the alloy system Pb-Sb, under conditions simulating casting. In Fig. 1, the essential features of a bidirectional growth apparatus are shown; horizontal freezing from water-cooled faces within a low-thermal-conductivity lavite boat is a reasonable simulation of an ingot section. Details such as the furnace and thermocouples are omitted in order to show the location of four permanent. magnets, each with a pole separation of 21 in. providing a central field of about 1000 Gauss. When coupled with a dc current imposed through appropriate connections made at the cooled faces, a flow of fluid is produced as shown schematically. This technique described by Pfann and ~orsi" is ideal for our purpose since the flow indicated is the same as that we observe to occur naturally in this system. Components of 99.999 pct purity were used for study and all due precautions were taken in alloy preparation to avoid contaminants. Sections of the specimens were taken to ensure results representative of the interior as well as the surface of specimens. All proportions of equiaxed and columnar regions were measured by tracing the etched grain structures onto graph paper and simply counting squares. Four alloys were examined at superheats of 40" * 5°C and 100" * 9°C. Preliminary tests had shown that no appreciable enhancement of structure was obtained with magnetic field alone, so that this condition is not reported; it should nevertheless be noted that other configurations of magnetic field will reduce convection and thus enhance columnar growth.'8 For the tests reported the magnetic field was applied to a specimen by bringing the four preassembled magnets to a position 2 mm from an outer tube immediately after the ingot was poured. The dc current of 30 amps passed through the sample throughout the entire solidification cycle, resulting in a power dissipation of 9 w per sq cm of interface. This may be compared to the evolution of latent heat of approximately 18 w per sq cm. Table I contains the results of this experiment in terms of the total area ratio, equiaxed/columnar grains, as a function of the field interactions, solute concentrations, and superheats employed. The total structure of the ingot is seen to be most influenced when both the field and current are applied simultaneously; when current acts separately, little effect may be noted in spite of the heat supplied. In addition, the change in structure from the no field-no current case to the field-current condition is more pronounced at the higher superheat, and the higher the concentration of antimony. An example of the grain refinement, as well as the increased equiaxed zone, is shown in Fig. 2. It is now important to prove that there is indeed an increase in fluid flow due to the presence of the field-current interaction; this is done by temperature measurements in the liquid metal. Let us consider a bidirectional casting in which heat is applied to and removed from the system, in such a way that rate of solidification is zero.* When a sensitive thermocouple

Jan 1, 1967

[Note.—The paper of Mr. Hoffman on " Practical Results in the Magnetic Concentration of Iron-Ore " (page 602); that of Mr. Langdon on "The Use of Magnetic Concentrates in the Port Henry Blast-Furnaaces" (page 599); and those of Mr. Landis on "The Determination of Iron in the Tails from Magnetic Concentration " (page 609) and "Note on Sampling Iron-Ore" (page 611), were all prepared as contributions to this discussion.] The papers of Mr. Langdon and Mr. Hoffman were presented. W. H. Hoffman, Croton Mines, N. Y.: I will add a few remarks, by way of answer to inquiries for further details. The Croton Mines are particularly well located for cheap mining. The ore-bed is very large, and so lies in relation to the railway tracks of the Harlem and other railroads that a very large proportion of our mining for several years to come can be done above these tracks. The concentrating-mill is now 400 feet from where we are working in the quarry. In blasting we never remove less than 2500 tons at a blast,

Jan 1, 1892

By D. C. Hilty, W. Crafts

A qualitative pseudoternary solidification diagram for the Fe-S-O system modified by manganese is proposed and supported by experimental derivation of an isothermal section at 1475°C and substantially 1 pct Mn in the solid-metal phase. The solubility of oxygen in liquid iron containing 1 pct Mn and sulphur contents up to 0.9 pct has been measured at 1600°C and found to increase as the sulphur content exceeds 0.15 pct. AS has been pointed out previously,' all oxide and sulphide inclusions in steel, excluding mechanically entrained matter, result from modifications of the basic Fe-S-O system. Therefore, one method of attack on the problem of the mechanism of deoxida-tion and inclusion formation is to examine the influence of deoxidizers on the Fe-S-O liquidus diagram. This approach has been adopted in work on the subject being carried out at the Metals Research Laboratories of the Electro Metallurgical Co. and has resulted in the postulation of types of solidification diagrams for the Fe-S-O system modified with common deoxidizers. This method has been of considerable assistance in interpretation of the factors affecting the formation of inclusions.' For the most part, however, these diagrams have been highly speculative. They were constructed primarily by inference from the pertinent binary and ternary systems and from the appearance of inclusions produced by specific deoxidizers. Moreover, since the systems contain four or more components, simplifying assumptions and qualifications were necessary in order to permit their representation as modifications of the Fe-S-O diagram. Consequently, experimental confirmation of the type of construction employed for these diagrams is desirable, and the present paper is concerned with such evidence. The addition of manganese to the Fe-S-O system was selected for initial investigation. Manganese is an important component of practically all steel and is, therefore, of fundamental interest. Because of its great affinity for sulphur, manganese has a more profound effect on the sulphide side of the Fe-S-O diagram than any of the other common deoxidizing eletments. In addition, more quantitative information pertaining to the contiguous binary and ternary systems involving iron, manganese, sulphur, and oxygen is available than for the other deoxidizers. Fe(Mn)-S-O Solidification Diagram Many of the side diagrams of interest in connection with this system are known. The Fe-Mn binary has been well established by several investigators;% the Fe-O system has been clarified by Darken and Gurry;' and FeO-MnO diagrams have been published by Herty,5 Andrew, Maddocks, and Howat,6 and by Hay, Howat, and White.7 The Mn-O diagram does not appear to have been derived experimentally, but the portion of 'it that is of interest can be visualized easily from a consideration of the melting points of Mn and MnO and the fact that a broad miscibility gap must exist between them. The ternary Fe-Mn-O diagram has been discussed by Benedicks and Löfquist,8 Wentrup,9 and by Körber and Oelsen.10 Experimental study of the Fe-Mn-O system has been carried out by Körber and Oelsen and to a lesser degree by Chipman, Gero, and Winkler,11 Hilty and Crafts," and others. On the basis of published information, then, an outline of the Fe-Mn-O liquidus diagram can be constructed as illustrated by Fig. 1. In this, as in all succeeding diagrams, transformations such as the ?-? reaction in iron have been ignored for purposes of simplification. The arrows denote falling temperature. The distinguishing feature of this diagram is the broad region of liquid immiscibility extending

Jan 1, 1955

By J. E. Steiner, J. M. Hodge, M. A. Orehoski

Ingots of four steels (1045, 1080, Ni-Mo-V, and Ni-Cr-Mo-V) were cast at pressures varying from about 1 to 760 mm of mercury, so as to obtain a range of hydrogen contents in each steel. The susceptibility of these steels to flaking was evaluated by cooling hot-rolled blooms at a range of cooling rates, varying from water quenching to slag cooling, and studying the occurrence of flaking as a function of cooling rate. The steels exhibited differences in susceptibility to flaking, and a tlzreshold value for hydrogen content for each steel was found, below which the susceptibility was very low and above which the susceptibility increased markedly with increasing hydrogen content. Mechanical property evaluations, metallogvaplzic exantinations, and X-my diffraction determinations o,t retained austenite were made on samples from the blooms. A mechanism of flaking which is consistent with the observed behaviors, the effects of hvdrogen content, and the differences in susceptibility among the steels investigated is postulated, based on the results of mechanical property evaluations and metallographic and X-ray diffraction studies. ThE important role of hydrogen as a factor in the occurrence of "flakes" or "hair-line cracks" in steel has now been established by many investigations. These have included investigations by steel producers and forging manufacturers, to whom the prevention of flaking is a very real and serious problem, and many research studies aimed primarily at establishing the mechanism of this behavior Several investigators3 have reported that steels cast at reduced pressures (absolute pressures of about 1 mm) not only are low in hydrogen content but are essentially insensitive to the formation of flakes. These investigations have shown that a general relationship exists between hydrogen content and susceptibility to flaking. The difficulty of obtaining suitable samples of steels of a given composition with the desired range of hydrogen contents, particularly in the relatively large sections in which flaking most commonly occurs, has been the principal obstacle to quantitative evaluations of these relationships. Steels with intermediate hydrogen contents between 1 ppm, and the 4ppm or higher of air-cast steels are generally not available in commercially produced steels. Laboratory procedures, in which the hydrogen is introduced into solid steel samples by heating in a hydrogen atmosphere under pressure, generally involve a limitation in the size of the sample which can be treated, and thus are not representative of the behaviors in large sections. The availability of a facility at the South Chicago Works of U.S. Steel, in which several ingots could be cast from a single heat of steel at total air pressures ranging from 0.25 to 760 mm of Hg, has made it possible to overcome this obstacle and to obtain ingots of a given steel covering the intermediate range of hydrogen contents desired. These ingots, furthermore, are of a size suitable for the production of product with section sizes large enough to be representative of the products in which flaking most commonly occurs in commercial production. In these experiments, this facility was used to study the relationships between hydrogen content and the susceptibility to flaking of four steels, two plain carbon steels at 0.45 and 0.80 pct C and two low-carbon alloy steels representing a medium and a rather high hardenability level. These flaking studies were supplemented by evaluations of mechanical properties and by metallographic studies on samples from the blooms, in order to obtain pertinent information on the factors other than hydrogen content which influence the susceptibilities of these steels to flaking. Based on the results of these tests, a mechanism for the initiation and propagation of the flaking cracks, which is consistent with the observed behaviors, is postulated. MATERIALS AND EXPERIMENTAL WORK Steelmaking and Conversion. To provide material for the investigation, five 29- by 35-in., hot-topped, big-end-up ingots were cast from each of four 80-ton, basic electric-furnace heats of four different steels (a 1045 steel, a 1080 steel, a Ni-Mo-V steel, and a Ni-Cr-Mo-V steel). A double-slag practice was used on all steels and the two plain carbon steels were Si-A1 deoxidized with an addition of 2 lb of A1 per ton, while the Ni-Mo-V and Ni-Cr-Mo-V steels were deoxidized only with silicon and

Jan 1, 1964

By Charles M. Romanowitz

The motivation for the art of dredging for placer mining can be compared in a slight degree to the spread of civilization which started in the Near East and spread both east and west. Dredging started with the "bag and spoon" dredge in the lowlands of Europe reportedly about 1565, went southeast to New Zealand where designs were developed for a bucket-line mining dredge known as the New Zealand type, and westward to the eastern United States where a dredge was developed and used exclusively for excavating. Then it moved to Montana, where it was first used for mining in 1895. The New Zealand-type dredge was imported into California in 1898 (Fig. 1) and was followed shortly by the Montana design. As today, these early dredges were equipped with continuous bucket- line chains, a treatment plant, and a means of waste disposal mounted on a wooden hull. Both types of dredges are complete mining units: they dig the formation, transport the dug materials, and concentrate the valuable ore. After sizing, the fines containing the ore are passed by gravity to the treatment unit, while the barren materials are discharged overboard. By digging the materials to be treated at the bow and depositing all the waste, at the stern, the dredges automatically advance to new reserves without presenting any transportation problems. The main differences between the two types are in the method of holding the dredge in the digging position and in the disposal of the tailings to the rear. The New Zealand type (Fig. 2) uses the headline system with a bow anchor for holding the dredge in the digging position and long tailing flumes or short stackers off the stern for disposal of the barren materials. The California type (Fig. 3) uses box girder spuds projecting into the ground in a vertical position at the stern of the

Jan 1, 1969

By AIME AIME

CORROSION of tanks, pipes and other equipment in the oil fields is becoming worse as the production of high- sulfur crudes in the Texas panhandle and west Texas areas increases. It has been estimated that .in certain fields of that State one tank out of every five has to be replaced every year because of the high sulfur content of the crude. One suggested method for combating tank corrosion is the use of .materials which have a high resistance to the corrosive action of hydrogen sulfide and high-sulfur crudes; aluminum is one of these materials. As a result, the United

Jan 1, 1929

By John L. Lamont, Walter Crafts

SECONDARY hardening in tempering has long been recognized as a typical characteristic of steels containing large amounts of carbide-forming alloys. These steels, when quenched and tempered, tend to soften somewhat after tempering at low temperatures, and to reharden at intermediate tempering temperatures before finally softening to low hardness. This behavior in tempering has been studied by many investigators, chiefly with respect to the secondary hardening of high-speed steels. The initial softening has usually been ascribed to decomposition of martensite and growth of iron carbide particles. The secondary hardening has been explained by formation of fresh martensite from residual austenite, formation of very fine alloy carbide particles and by precipitation hardening of metallic compounds in the ferritic matrix. However, factors derived for the calculation of tempered hardness in low-alloy steels1 indicated only a tendency toward retarded softening rather than a discontinuous rehardening. A study was, therefore, made to determine whether fresh martensite from residual austenite and precipitation hardening are essential to rehardening and the degree to which tempered martensite could be rehardened by precipitation of alloy carbides. The mechanism of carbide rehardening was also investigated to determine the nature of the process. The causes of secondary hardening in high-speed steel have received serious consideration for about thirty years. Among the earlier workers Bain and Jeffries2 in 1923 recognized residual austenite as a significant factor, but in addition, emphasized the effect of the formation of alloy carbide particles of "critical" size. They conceived that freshly quenched martensite forms low-alloy iron carbide at low tempering temperatures; with further tempering the iron carbide is then modified by alloying elements that can diffuse most readily at intermediate temperatures (850°F); and that the iron carbides grow in size by coalescence so that the steel tends to lose hardness. At higher tempering temperatures carbide stability rather than alloy availability becomes the controlling influence and in high-speed steel "iron-tungsten carbide is the most stable one and forms to the elimination of the earlier formed carbides. . . . The iron-tungsten carbide particles reach approximately the size for critical dispersion after a short reheat at 1100°F." This concept, the formation of alloy carbide nuclei, redissolving of the iron carbide, and diffusion of carbon to the alloy carbide, was restated for vanadium steel in 1932 by Houdremont, Bennek, and Schrader.3 Subsequent studies have confirmed that iron carbide changes to alloy carbide at 1000 to 1100°F, but the mechanism of the process has received little consideration .

Jan 1, 1948

By Albert A. Smith

The creep properties of metals have assumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Institute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investigate creep phenomena because of the simplicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals. Material The creep tests of this investigation were all made on high-purity lead (99.9998+ Pb) in which the only impurity that could be detected by spectrographic and chemical means was approximately 0.0001 per cent Fe. Flat strips, 0.750 in. wide by 0. 100 in. thick, were prepared by extruding 2-in. dia. cast billets at a temperature of 250°C. This gave a material of 2 to 3 mm. average grain size with a tensile strength of j.400 lb. per sq. in. when tested at a straining rate of 5 per cent per minute. With this extremely soft material, great care was necessary in handling the specimens, to avoid distortion and subsequent recrystallization. The creep tests at 30°C. were conducted in a constant-temperature room, specially built for the purpose in the basement of an office building in which there was no moving machinery, and no vibration was detectable under the most severe conditions of shock in the adjacent surroundings. The room was well insulated and heated electrically, control being by means of a de Khotinsky regulator operating a relay. Maximum temperature variation over a period of several years has been ± 1/2°C. Specimens of the extruded strip, 16 in. long, were used for test purposes with no reduced gauge section, thus eliminating any distortion due to machining. The method of clamping and supporting the specimens is shown diagrammatically in Fig. 1. The gauge marker for the measurement of extension consisted of an aluminum strip, 0.050 in. thick by 0.75 in. wide, one end of which was ground and sanded to a precise knife-edge and fastened to the specimen by suitable pins. After the strip was fastened in place a fine scratch was inscribed just below the knife-edge by means of a sharp teasing needle. Just below this gauge scratch a short vertical mark was made so that the same point could be located and read each time. Several hundred specimens have been prepared by this method, and it was found that with experi-

Jan 1, 1941

By Albert A. Smith

The creep properties of metals have assumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Institute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investigate creep phenomena because of the simplicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals. Material The creep tests of this investigation were all made on high-purity lead (99.9998+ Pb) in which the only impurity that could be detected by spectrographic and chemical means was approximately 0.0001 per cent Fe. Flat strips, 0.750 in. wide by 0. 100 in. thick, were prepared by extruding 2-in. dia. cast billets at a temperature of 250°C. This gave a material of 2 to 3 mm. average grain size with a tensile strength of j.400 lb. per sq. in. when tested at a straining rate of 5 per cent per minute. With this extremely soft material, great care was necessary in handling the specimens, to avoid distortion and subsequent recrystallization. The creep tests at 30°C. were conducted in a constant-temperature room, specially built for the purpose in the basement of an office building in which there was no moving machinery, and no vibration was detectable under the most severe conditions of shock in the adjacent surroundings. The room was well insulated and heated electrically, control being by means of a de Khotinsky regulator operating a relay. Maximum temperature variation over a period of several years has been ± 1/2°C. Specimens of the extruded strip, 16 in. long, were used for test purposes with no reduced gauge section, thus eliminating any distortion due to machining. The method of clamping and supporting the specimens is shown diagrammatically in Fig. 1. The gauge marker for the measurement of extension consisted of an aluminum strip, 0.050 in. thick by 0.75 in. wide, one end of which was ground and sanded to a precise knife-edge and fastened to the specimen by suitable pins. After the strip was fastened in place a fine scratch was inscribed just below the knife-edge by means of a sharp teasing needle. Just below this gauge scratch a short vertical mark was made so that the same point could be located and read each time. Several hundred specimens have been prepared by this method, and it was found that with experi-

Jan 1, 1941

THE. extraordinary volume of work done in this period, and the multiplicity of subject matter, make a year-by-year historical account undesirable, if the account is not to be an assembly of unrelated fragments. We shall, instead, undertake to narrate the development in this period of each of the branches of the subject separately, hoping that their interrelations will be self-evident. There is a certain arbitrariness in the selection of subject matter in the following sections. The development of important engineering alloys-for example, high-speed steel-is disregarded, for it is the primary purpose of this account to relate the advances in ideas, the growth of the science of metals; other historical accounts relate these parallel advances. Nor are advances in techniques stressed, though occasionally the most important are noted; nor is the progress described in allied fields such as welding, cutting, etc.; for though these developments have very frequently made possible the advances herein related, they are far too numerous to recount in anything short of a ponderous volume. There is a more serious arbitrariness, however; it is not an easy matter to draw the boundaries of physical metallurgy, and some contiguous subjects have been omitted that perhaps should have been included, such as, for example, corrosion, gases in metals, the magnetic behavior of metals and alloys, and certain other fields in the physics of metals. REACTIONS IN ALLOYS--DIFFUSION Many of the reactions occurring in alloys proceed by the operation of the process of diffusion in the solid state: the annealing of mixed powders to form alloys, the homogenization of castings or forgings, the freezing of alloys, the treatment of clad metals, the loss

Jan 1, 1948

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By D. F. Hewett

ALTHOUGH most persons will agree that an individual or a nation can profit from the experience of other individuals or nations, there is always room for debate over the degree of similarity of their past and present conditions and of their future problems. Noting the increasing interest that Americans are showing in our mineral problems, I have felt that we could profit from reviews of the experiences in mineral exploitation acquired by the industrial nations of Europe. Whether we can learn much from Europe's experience in exploiting such minerals as petroleum may be debatable, but certainly, with a record of metal production extending back nearly 3000 years, Europe should hold much of value for America. A trip to Europe in 1926 permitted me to visit 28 mining districts, of which about half are now or have been in times past outstanding sources of several metals. The districts range from England to Greece and from Spain to Poland. To summarize briefly my impressions of these mining districts, as well as such reactions to the thought and life of Europe as so short a visit permits, I shall only venture the opinion that Americans can review with great profit the ideas and actions of Europeans, with regard not only to the production of metals but to many expressions of life. I believe that America has made and is making new contributions to the art of living, as well as to the arts of mining and metallurgy, but in so far as Europe is and has been a laboratory of economic, social and political experiments, the results she has attained deserve the thoughtful attention of America. I have come to believe that many of the problems that harass Europe lie in our path not far ahead. I have therefore hoped that a review of metal production in Europe in the light of its geologic, economic and political background may -serve to clear our vision with regard to our own metal production.

Jan 1, 1929

By W. F. Hosford

A series of aluminum single crystals was subjected to axially symmetric flow by drawing through dies. The orientation dependence of the drawing stress, which indicates the resistance to this type of flow, compares reasonably with predictions of Taylor and of Bishop and Hill. Measured lattice rotations likewise are generally consistent with theory. The most successful analyses of the plastic behavior of polycrystalline metal and its relationship to single crystal behavior are those of Taylor1-3 and of Bishop and Hill.4-6 The purpose of this paper is to provide a critical test of some of the basic assumptions involved in these theories. Both treatments apply to fcc metals and assume the shape change of each grain in a polycrystal to be the same as that of the polycrystal as a whole. Thus for a randomly oriented polycrystal extended under uni-axial tension each grain is assumed to undergo axially symmetric flow. dey = dez = -1/2dex, deyZ = dezx = dexy = 0 [l] where x, y, and z are a set of orthogonal axes, x being the tensile axis. Although [011.] oriented grains in bcc and fcc metals may depart markedly from this ideal behavior,7,8 the assumption is probably quite reasonable for most grains. Under a uniaxial tensile stress, ox, the work dW per unit volume expended in producing an increment of axial strain dex is, dW=oxdex [21 Since this work is expended in slip, dw =STi dyi 131 where Ti and yi are the shear stress and shear strain on the active slip systems. In both analyses Ti is taken to be the same on all slip systems, and dependent only on the total prior shear strain on all systems, so dw = Tdy [41 where t is the shear stress required for slip and y is the sum of the shear strain yi on all slip systems. Combining 121 and [4] and defining M = oX/T The ratio M is a generalized Schmid factor. It relates the tensile stress required for axially symmetric flow, ox, to the basic shear stress, 7, and it also expresses the ratio of crystallographic strain, y, to the tensile strain, Ex It depends only on the orientation of the crystal. Taylor evaluated M for various orientations by finding the least value of dy/dEx which could satisfy the shape change. Bishop and Hill, on the other hand, found M by considering the relative work (1/T)dW/dEx expended by stress states which could activate enough slip systems to produce the shape changes. The results of both methods appear to be equivalent, although certain omissions were made in Taylor's original work. The orientation dependence of M, calculated by the second method,9 is shown in Fig. 1. Taylor used the average 2= 3.06 for all possible orientations to predict the tensile stress-strain curve (oxvs Ex) for a random polycrystal from the shear stress-strain curve (t vs y) of a single crystal. Changes in M from lattice rotation were neglected so points on the ox vs ex curve were simply taken at ox = 3.06t and e = y/3.06 from corresponding points on the t vs y curve. Recent extension of the analyses of Taylor and of Bishop and Hill to crystallographically textured metals has been used to relate plastic anisotropy to textures, and to predict the potential texture hardening that could result from texture control.9 Unfortunately there have been relatively few experimental tests of the underlying theory. Taylor found that the tensile stress-strain curve of polycrystalline aluminum did agree reasonably well with that predicted from a single-crystal T-y curve. Had the single crystal undergone easy glide, how-

Jan 1, 1965

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By Raymond D. Sloan

Development and exploration in Oklahoma showed a definite increase in 1941 over 1940 in production, wildcat activity and total well completions. Geological and geophysical work continued and possibly increased slightly in amount. Oklahoma retained third place in the ranking of oil-producing states of the nation, topped only by Texas and California, and followed by Illinois in fourth position. Production averaged 416,800 bbl. daily, a 1.7 per cent increase, as compared with 409,900 bbl. daily for the year 1940. Maintenance of the state's relatively stable producing rate resulted from the discovery of numerous small pools, the recombing of old areas, the establishment of new producing horizons, and the drilling of an increased number of marginal wells. The market for the Mid-Continent crude was strengthened materially to meet the increased demand. Coincident with a deeline in production in Illinois, shipment of Oklahoma-Kansas crude to the eastern points averaged 453,000 bbl. per day, an increase of 49.4 per cent as compared with 1940. The movement south amounted to an average of 42,000 bbl. per day, a loss of 41.7 per cent. Secondary-recovery programs in Oklahoma were given more consideration, operators realizing that in the future many pools would necessarily have to resort to this type of operation. Five permits for water-flooding were issued by the Corporation Commission during the year. These projects were in Rogers, Wagoner and Nowata Counties, in the shallow northeastern area, which has relatively extensive development of this type in the Bartles-ville sand at from 600 to 1000 ft. in depth. Gas repressuring of an individual lease in the 35-year old Glenn pool, Creek County, proved relatively successful, and after a year's operation was extended to cover a much larger area, with several operators participating. More of this type of work is expected in the future; however, it was given an initial setback when the legislative proposal authorizing secondary recovery in the Wilcox zone of Oklahoma's largest pool, the Oklahoma City pool, was pigeonholed by the committee. A continuation of the low discovery rates within the state would possibly lead to a revival of interest in the project. Many pools formerly classified as prorated areas were removed from this classification and transferred into the group of settled production. At the close of the year the issuance of the Federal Conservation Order M-68 and the interrelated Preference Rating Order P-98 caused a sharp decline in drilling operations, which is expected to continue until such operations are stabilized at a lower rate. The ultimate effect of these two orders on discoveries, production and reserves is a matter of speculation and conjecture. During the year, 2110 new wells were drilled, an increase of approximately 18 per cent as compared with the previous year. Of the total, 1235 were oil wells with a combined initial potential of 342,754 bbl. daily, 178 were gas wells with a total

Jan 1, 1942

By J. R. Hunter

Current trends in mining practices within the United Kingdom, with particular reference to longwall retreating systems in thick and steeply pitched coal seams at depth, are explained. Various successful mining layouts are considered with their associated machinery and operation, together with the future trends in mining practices to obtain higher outputs. Environmental difficulties are tabled and discussed, including strata control, methane emmision, and dust prevention, together with some modified systems and techniques to overcome them. The problems associated with developing and maintaining a continuance of longwall panels are outlined. The constraints on technical designs and output achievement imposed by noncommercial factors are also considered.

Jan 1, 1978

By Harrison Schmitt

SINCE the U. S. Geological Survey published the data on the Central Mining District collected by Lindgren and Graton1 and by Paige2 much new information has been obtained by development and mapping, but none of it had been published until recently when Kniffin3 published on Fierro, Lasky4 on the Ground Hog mine, Thorne5 on Santa Rita and Landon6 filed a thesis on the Fierro-Hanover-Santa Rita area at the Uni-versity of Chicago. During the years 1927-1930 much of the writer's time was spent in mapping the geology and ore deposits of this district, particularly in the area of the zinc deposits at Hanover. Some of the data collected are presented here. Previous publications have been freely drawn upon and additional data used that were generously supplied by L. M. Kniffin, Wilfred Wright and Gerald Ballmer. Thanks are due Augustus Locke, Samuel G. Lasky, Kniffin, Wright and Ballmer for suggestions and critical readings of the manuscript, and to the Empire Zinc Co. (a subsidiary of the New Jersey Zinc Co.) for the privilege of publishing material compiled largely at its expense. The relation of the Central. or the Santa Rita-Hanover-Fierro district to the Silver City district is shown on Paige's geologic map in the Silver City folio.7 Granodiorite porphyry and quartz-monzonite porphyry

Jan 1, 1933

By P. D. Bush, E. H. Gates, M. D. Vijayaraghavan, L. F. Engle

The process developed over the last few years by Republic Steel Corporation in conjunction with Colorado School of Mines Research Institute has been used as a basis for the conceptual engineering of full size plants. The paper will cover the equipment design criteria, equipment design itself, and the integration of the complex unit operations. There are unique features of agitation and use of gas media through- out. The paper will provide an illustrative example of the process requirements for a variety of raw material feeds. It will discuss the materials of construction approach required.

Jan 1, 1973