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By John C. Sawyer

The mechanism of catastrophic oxidation of chromium and 446 stainless steel is examined. Data are presented to show that accelerated oxidation of these two materials, as caused by lead oxide, can occur in the absence of a liquid layer contrary to presently accepted theory. An alternate theory is proposed in which the rate of accelerated oxidation is a function of the rate at which lead oxide destroys the protective oxide formed on the base metal. An example of the application of the theory is given for the catastrophic oxidation of chromium in the presence of lead oxide. WHEN stainless iron-, nickel-, or cobalt-base alloys are heated in air to moderate temperatures in the presence of certain metallic oxides, oxidation will proceed at an accelerated rate. This phenomenon, often called "catastrophic oxidation", is most pronounced for the stainless steels. With these alloys the condition is so severe that large masses of oxide will form on the surface of the alloy in 1 hr or less at temperatures of 1200o to 1700oF. While a number of oxides are known to cause this effect, PbO, V2O5, and Moo3 are the most familiar, having been the subject of one or more investigations which have appeared in the literature.1-7 In presenting the results of these investigations, many of the authors have offered possible explanations to account for the more rapid rate of oxidation observed; however, the liquid layer theory as proposed by Rathenau and Meijering 2 has been the most commonly accepted mechanism. The liquid layer theory proposes that a low-melting oxide layer is formed on the surface of the alloy as the result of the interaction of the alloy oxide and the contaminating oxide. When the temperature of oxidation is above the melting point of the oxide on the surface, a liquid layer will form and oxidation will proceed at an accelerated rate. At temperatures below the melting point of the surface oxide, oxidation will proceed more slowly in the normal manner. It is argued that the rates of diffusion of oxygen and metal ions through the liquid layer are extremely rapid thereby accounting for the high rate of oxidation. Various experimental data have been presented to show that the temperature at which accelerated oxidation first becomes apparent coincides with the melting point of the eutectic oxide which would be present on the surface. Some exceptions have been observed, e.g., silver will oxidize in the presence of Moo3 at temperatures below the lowest melting eutectic; on the other hand, stainless steel will not be catastrophically oxidized at 1500oF in a molten bath of PbO and SiO2. In reviewing the various theories which have been used to explain catastrophic oxidation, Kubaschewski and Hopkins 8 favor the liquid layer theory, but note that, ".. .as experimental observations are not altogether in agreement with this theory (liquid layer theory), one should consider it a necessary but not a sufficient condition." In contemplating the liquid layer theory, it appears that sufficient evidence has not been presented to establish the theory beyond question. As a means of further clarification, a program of research was undertaken to determine in greater detail the mechanism of accelerated oxidation as caused by lead oxide. The first part of the program deals with a comparison of the oxidation of both AISI 446 stainless steel and chromium metal in the presence of lead oxide, vs the oxidation of these two materials in air alone. These comparisons are made at a number of different temperatures, most of which are below the melting point of the surface oxides. The second part of the program is concerned with a presentation of an alternate theory of accelerated oxidation exemplified by the system Cr-PbO-Air. PROCEDURE AND RESULTS Several experimental methods are commonly used to follow the progress of oxidation. One of these, the weight-gain method, was chosen for this work. This procedure requires that a specimen of the alloy be weighed, oxidized for a given period of time at an elevated temperature, and reweighed—the difference between the two weights being noted. The weight gain of the specimen represents the amount of oxygen acquired from the atmosphere to transform a portion of the specimen to oxide. In those cases where there is a tendency for the specimen or oxide to volatilize at the testing temperature, additional data must be collected so that a correction factor can be determined. This factor must be applied to the weight change in order to ascertain the actual amount of oxidation which has taken place. The specimens used for this work were 1 1/2 in.

Jan 1, 1963

By Arthur Redfield

IN ESTIMATING the unmined petroleum reserves of Central America, it is not feasible to employ the methods that have been worked out in the oil fields of the United States. No producing wells have been brought in and no drilling sections have been made public. It is accordingly necessary to fall back on a crude "barrels per square mile" estimate. The method chosen is a comparison of the structure of the foreign field of unknown reserves with that of some supposedly analogous North American field of which the reserves have been estimated. This method makes no pretense at scientific accuracy; bit furnishes a working basis for an estimate. The areal geology of Central America is illustrated in the map prepared by Sapper and more recently in the geologic map of North America accompanying U. S. Geological Survey Professional Paper No. 71, "Index to the stratigraphy of North America." Disregarding for the present the Arrow Quaternary coastal plains and alluvial deposits of the river valleys, three chief zones may be distinguished. These are: A zone of late eruptive and effusive rocks; a zone of highly folded pre-Cambrian(?) or early Paleozoic crystalline schists and slates, considerably intruded by pre-Tertiary plutonic rocks; and a zone of more or less folded sediments, chiefly of Cretaceous or Tertiary age. The zone of late eruptive and effusive rocks of Central America begins in southeastern Chiapas, Mexico,. and extends, with increasing breadth, across southern Guatemala, across practically the whole of El Salvador, and across southern Honduras to the valley of Rio Goascorán, where the igneous zone attains a width of about 100 mi. (160 km:) East of the Goascorán Valley late eruptives and effusives play a subordinate part, being confined largely to the Departments of Valle and Choluteca. Dikes and sills of igneous rocks intrude the sedimentary formations of central and northern Honduras.

Jan 7, 1922

By G. L. Fisher, R. H. Geils

The effect of small amounts of columbium (<0.01 to 0.10 pct) on the ?-a transformation occurring during the continuous cooling of a low carbon Ni-Cu steel was investigated. Dilatometer specimens were aus-tenitized at 950" and 1068?C and cooled at 17? and 375 C° per min. Columbium caused a marked depression in the ?-a transformation temperature except when cooling at the slower rate from 950°C. The effec of columbium on the transformation temperature was greater the higher the austenitizing temperature and rate of cooling. A maximum depression of 92 C" was observed. Metallographic examination of specimens of <0.01 and 0.07pct Cb steels heated at 1200°C for 1 hr and cooled at various rates showed that columbium had a major effect on the ferrite morphology. The fer rite in the columbium -free steel remained equiaxed at cooling rates as high as 440 C? per min while the columbium-bearing steel exhibited mixed structures o equiaxed and bainitic ferrite at cooling rates as low as 130 C° per min. The ? grain boundaries in the columbium -free steel provided the ferrite nucleation sites in rapidly cooled specimens. There was a complete absence of nucleation at these sites in the colum bium-bearing steel. It is concluded that columbium depresses the transformation temperature by suppressing ferrite nucleation at the austenite grain bound-aries. In this respect the effects of columbium are analogous to those of boron in low C-Mo steels. It is well known that small columbium additions can substantially strengthen plain carbon steels. As little as 0.02 pct Cb can increase the yield strength of mild steels by 10,000 psi.1 A fine precipitate of CbC has been observed in columbium-bearing steels2 and is generally thought to be responsible for the strengthening. Little attention has been devoted to the effect of columbium on the ?-a transformation. Webster and woodhead3 have studied the effect of columbium on the isothermal proeutectoid ferrite reaction in mild steels. They found similar transformation behavior in steels both with and without columbium additions. However, as the austenitizing temperature increased, the incubation time for the start of the ferrite transformation became longer in the columbium-containing steel. Morrison1 found that the addition of 0.03 pct Cb to a C-Mn steel lowered the transformation temperature by 50 C° during cooling from 1200°C at a rate of 80 C" per min. The strengthening effect of columbium has recently been utilized in an age-hardenable, low-alloy steel containing copper and nickel.4 A small amount of columbium has a substantial effect on the as-rolled strength of this steel. By increasing the columbium level from <0.01 to 0.13 pct the as-rolled yield strength is increased by 15,000 psi. Columbium also significantly lowers the ?-to-a transformation temperature of this steel during continuous cooling from the austenitizing temperature. Because of the low carbon level in this steel (0.05 pct max), it is almost entirely ferritic. Thus, it offers the opportunity of studying the effect of small columbium additions on the proeutectoid ferrite reaction. Of particular interest in this study was the reason for the marked lowering of the transformation temperature by columbium during continuous cooling. EXPERIMENTAL PROCEDURE Materials. The compositions of the steels used in this investigation are shown in Table I. The steels were 30-lb air induction melts. They were forged to 4 by 8 by 1 in. plate at 1230°C, air cooled, and then reheated to 1230°C and cross-rolled in two passes to in. plates. Dilatometry. A Leitz Bollenrath dilatometer was used to record the transformation during continuous cooling from two different austenitizing temperatures. The dilatometer specimens were + in. in diam and 2 in. long. Oxidation and decarburization of the specimens was prevented by maintaining a small positive pressure of dry argon in the dilatometer furnace and by plating the specimens with 1 mil of Cu. For the lowest cooling rate, 17 C" per min, the temperature of the specimen was measured with a Pt-Pt 10 pct Rh thermocouple placed in a & in. diam well in the center of the specimen. During air cooling, 375 C° per min, this method of measuring the temperature interfered with the operation of the dilatometer. However, it was found that the temperature of the specimen could be measured accurately by placing a thermocouple in an identical specimen in a holder adjacent to the one being used to operate the dilatometer mechanism. The dilation-temperature curves were recorded on photographic film and then converted to volume percent ferrite-vs-temper-ature curves. The cooling rates obtained with the dilatometer are shown in Table 11. Cooling rates of

Jan 1, 1970

By J. P. Neumann, L. Raymond

At temperatures near 1000°C, only the (112) (111) slip systems are operatire in tungsten. Therefore, the substructure introduced into the billet upon rleforming a single crystal by rolling at 1000 "C can be controlled by proper selection 01. processing ral&apos;iubles. Using a reduction of 10 pct pel- pass, the (001)[110] and the (110)[001] crystals will deform by duplex slip rip to a 50 pet reduction in thickuess. These rolled single-crystal sheels are characlerized by anisotropic hardening, retention of ductility with warm working, lattice bending which is related to the conlacl (angle, and macroscopic dimensional changecs in the length bid not the width of the billet. When several slip systems become operative, a greater degree of work hardening is itztvoducetl into the crystal. This rolling- condition is characlerized by isotropic hardening, loss of ductilily with warm working, complex lattice distortions, and macro-scopic dimensional changes in both the length rind Width of the billel. IN tungsten, the {1 10}(111) slip systems are operative below room temperature,&apos; while above 700°C only the {112{ (111) slip systems are observed.2,3 In the transition region, i.e., room temperature. both systems appear. It is the purpose of this investigation to show that tungsten single crystals deformed by rolling at a temperature where only one slip system is operative generate dislocation substructure which depends on the crystal orientation. For a specific crystal orientation. the resulting dislocation substructure can be further influenced by modifying the rolling procedure. Crystals oriented for multiple slip display less substructural sensi- tivity to modifications in processing techniques than do single crystals oriented for duplex slip. Under simple slip modes of deformation, very little work hardening is introduced into a rolled single-crystal sheet. Mechanical properties such as room-temperature strength. ductility, and hardness are used to confirm the existence of the different work-hardened conditions generated within the crystal by modified warm-rolling techniques. EXPERIMENTAL PROCEDURE Material. Single-crystal billets of four different crystal orientations. grown by the Arc-Verneuil technique. were ground to a size of 0.25 by 0.375 by 3 in. In terms of their rolling plane and rolling direction, the billets had the following orientations: (1101 [001 ] (110) [110] (001) [110] (001) [100] The actual orientation of all crystals was within 5 deg of the ideal orientations. The typical impurity content of the crystals is given in Table I. Polishing and Etching. Polishing was done elec-trolytically in a 20 g per liter aqueous solution of NaOH at approximately 10 v. It was established by the Laue back-reflection X-ray technique that the surface damage due to grinding and cutting operations with a diamond wheel did not exceed 0.001 in. Therefore after each cutting or grinding operation at least 0.002 in. was removed electrolytically from the surface in order to eliminate surface effects. By lowering the voltage to 3 v, subgrain boundaries and individual dislocations are identified in agreement with Berlec 4 where the etch-pit traces on a cubic plane form a square. The etching time was about 5 sec at room temperature. Rolling. Rolling was carried out on a Loma 2-high mill (Model 600). The peripheral velocity of the 6-in.-diameter rolls was 500 in. per min, with the surface temperature of the rolls about 400° to 450° C The billets were heated before each pass for 30 min in argon to 1000 C. Oxidation of the crystals during rolling in air resulted in a thin layer of greenish-yellow WO 3 This oxide was removed after each pass by immersing the crystals for a few minutes in a boiling NaOH solution. Prior to the initial rolling pass, a surface layer of 0.001 in. was removed by polishing. The crystals were then annealed in vacuum (10-4 torr) at 2400 C for 30 min. All crystals were rolled in the same direction; i.e., the same end was always introduced into the rolls. The rolling program was conducted in

Jan 1, 1965

By G. A. Beiswenger

The application of the law of supply and demand to the sale of crude oil is generally conceded, but the motives underlying the buyer&apos;s (refiner&apos;s) demands are not always obvious to the seller (producer). In some cases this obscurity has led to the conclusion that the refiner may be unnecessarily particular when he selects one crude and rejects another. This preference, however, is very largely the reflection of the refiner&apos;s product demands and the quality of the stocks obtainable from the selected crude. The purpose of this paper is to point out critical characteristics of the major classes of refined products and to show how crudes vary in their suitability for such products. With relatively few exceptions, available processing methods and addition agents make it theoretically possible to produce any type of refined product from any crude source, although it may not be economi-cally sound to do so. The widespread application of thermal cracking for converting higher boiling stocks into gasoline is well known. More recently cracking and refining in the presence of catalysts9 have been developed, as well as various processes for polymerizing lighter hydro-carbons into gasolines having desirable characteristics.6 For several years, selective solvents have been applied commercially to refining inferior quality kerosene, Diesel fuel and lubricating oil distillates .3 Improved methods for refining lubricating oils from crude residua,4 formerly suitable only for fuel, are now in use and a number of special solvent processes are available for dewaxing lubricating oils to low pour point.5 These improved refining methods have been developed not only to meet the demand for improved product quality but also to enable the refiner to obtain quality products from crude sources that would not yield such products by the older refining methods. In many cases, the utilization of these modern refining tools necessi-tates an appreciable expenditure for equipment as well as added manufac-turing costs, and their application therefore must be justified economically. Despite the availability of such tools, the added processing costs involved and yields obtainable may render their application entirely impractical. To illustrate this point, inspections of typical cuts from various crudes

Jan 1, 1940

The paper relates to the laboratory and pilot plant studies that have been carried out by Sherritt Gordon Mines Ltd., Metallurgical Research Div., in developing the ammonia pressure leach process for extracting Cu, Ni, Co, and S from high grade Ni concentrate produced from Lynn Lake ores and describes in some detail the chemistry of the process. In the leaching stage air, ammonia, and sulphide minerals react in a sequence of inter-related steps to produce soluble amines of Ni, Cu, and Co in a solution containing sulphate, thiosulphate, polythionate, and sulphamate ions and a controlled amount of free ammonia, the iron and other components of the concentrate remaining as an insoluble residue which is separated from the leach solution by filtration. The pregnant solution produced in leaching is further treated by boiling to precipitate and remove Cu as cuprous sulphide, leaving a copper-free solution with a composition suitable for subsequent precipitation of Ni and Cu by H,

Jan 3, 1955

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony&apos; states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By P. G. Shewmon, F. N. Rhines

THE determination of the self-diffusion coefficient of magnesium has been made possible recently by discovery1-1 of a radioactive isotope, Mg28 having a half-life of 21.3 hr,1 and subject to manufacture in useful quantity. In the present research this material was condensed from the vapor phase upon a surface of high purity magnesium. The progress of diffusion of the tracer atoms into polycrystalline magnesium was followed by machining layers and measuring the change in the intensity of radiation as a function of the distance of each layer from the surface. The self-diffusion coefficient was found to be 2.1 X 10-8 sq cm per sec at 627°C, 3.6 X 10-9 sq cm per sec at 551°C, and 4.4 X 10-10sq cm per sec at 468°C; the activation energy is about 32,000 cal per mol. Experimental Procedure Since there was no other published measurement of a diffusion velocity in any magnesium-base material, is was necessary to employ a number of new experimental techniques. The short half-life of Mg28 made it necessary to complete the entire experimental procedure within three or four days. This meant that the work had to be done where a cyclotron was readily accessible and that all operations, prior to the diffusion heat treatment, had to be so designed as to minimize their time requirements. Unusual problems were imposed also by the chemical reactivity of magnesium, its high vapor pressure, and the fact that no satisfactory method for elec-trodepositing magnesium on magnesium is presently available. Finally, the machining and handling of the easily air-borne radioactive-magnesium chips involved certain health hazards, resulting in the need for further experimental restrictions. Preparation of Mg28 The Mg28 was produced in the Carnegie Institute of Technology syncrocyclotron by the neutron spallation of chlorine.5 his involved bombarding a 2 gram crystal of high purity NaCl with a beam of 350 mev protons for a period of 2 hr, after which the crystal was dissolved in warm water and the Mg28 was concentrated and purified by chemical means (see Appendix). About 50 microcuries of Mg28 thus were obtained in the form of magnesium oxinate (8 hydroxyquin-olatc?), which was ignited in air to produce MgO. This in turn was reduced to magnesium metal vapor, by the method of Russell, Taylor, and Cooper," in the vacuum apparatus shown schematically in Fig. 1. Here the essential part is a tantalum ribbon, slightly dished to receive the MgO. The ribbon, pre- viously outgassed at high temperature, is heated to about 1700°C by passing an electric current through it, whereupon tantalum oxide is formed, magnesium vapor is released almost instantaneously, and condensed partly upon the diffusion sample. Diffusion-Sample Preparation: Hot-extruded magnesium rod, 21/32 in. round was used in making the diffusion specimens. The magnesium analyzed as follows: 0.004 pct Al, 0.027 pct Fe, 0.040 pct Mn, 0.0004 pct Cu, 0.0002 pct Ni, and less than 0.01 pct Ca, 0.0004 pct Pb, 0.0011 pct Si, 0.001 pct Sn, and 0.001 pct Zn. A brief study of the crystal texture of this material revealed a sharp fiber texture with the (001) plane roughly parallel to the extrusion axis. Cylindrical samples 1/2 in. long by 5/8 in. were machined from this rod, the end faces dressed on 3/0 emery, and lightly etched with 20 pct HC1 in water. These samples then were annealed for at least twice the intended time of diffusion, at the intended diffusion temperature, in order to stabilize the grain structure at about 1 mm average diameter. The annealing treatments were conducted in argon in the same apparatus and in the same manner as the subsequent diffusion treatments, which will be described presently. Thus, a strain-free plane surface was produced, but there remained a layer of MgO which had largely to be removed before the layer of Mg28 was deposited. Most of this layer was taken off by two light passes over 3/0 emery paper. The balance of the oxide and a thin layer of metal were then removed by etching 5 to 10 min in 4 pct nital (4 pct HNO3 and 96 pct ethyl alcohol) made with absolute alcohol. There followed immediately three quick rinses in: 1-49 1/2 pct methanol, 49 1/2 pct acetone, and 1 pct formic acid, 2-50 pct methanol and 50 pct acetone, and 3-pure benzene. This procedure is essentially that of Sturkey.7 The resulting surface, which was of almost elec-tropolished brightness, remained plane and was free of cold work. It could be kept clean by storing under benzene, or in a desiccator; short exposure

Jan 1, 1955

By Robert Pack

INTRODUCTION SOONER or later in the development of any natural resource it becomes highly desirable to know the quantity of this resource in the country as a whole, as well as of the part that is being developed, for the general course and. conduct of the development work must be governed to some extent by the total supply available. An accurate estimate of the quantity of any natural resource is difficult to make; yet if one is diligent enough one can obtain a pretty accurate idea of the quantity of marketable timber, the acreage of tillable land, or the horsepower that may be developed from the streams, for these are things that may be measured. But any attempt to estimate the quantity of some mineral in the ground appears to enter the realm of imagination and it seems that the estimate can be nothing more than a blind guess. It may appear to be especially futile to attempt to determine the quantity of oil and gas that is available in the ground, for these minerals are so vagrant that even if the quantity now available should be known quite exactly, the quantity that will eventually be obtained may be much less, for certain losses in the extraction of both oil and gas are unavoidable, and just what these losses will be cannot be predicted. Though necessarily inaccurate, estimates of such mineral reserves are, however, of distinct value, for they summarize the existing knowledge of the deposits of the mineral and thus enable those who are interested in some industry that depends in one way or another on this mineral to formulate a rational commercial policy. Some time ago, when the price of gasoline suddenly rose in a rather spectacular manner, the writer was one of the U. S. Geological Survey geologists called upon to help to estimate the quantity of oil that could be obtained in the United States, for the fear had become widespread that perhaps the rate of increase in the price of gasoline was a measure of the rate of depletion of the supply of petroleum. It thus became his

Jan 8, 1917

By Max Y. Seaton

THE scope of this paper will be limited to finished materials that contain a large preponderance (around 80 per cent or more) of magnesium oxide. The large and commercially important production of refractory dolomite and modified dolomites is not discussed here, and the production of magnesium basic carbonate for use as a heat insulator is barely mentioned. The discussion is confined mainly to magnesias produced in comparatively great quantity by direct processing of naturally occurring raw materials and hence excludes secondary or highly purified products such as pharmaceutical products or U.S.P. light and heavy calcined magnesias of commerce. NOMENCLATURE The nomenclature of the magnesia products that will be discussed is somewhat confusing, in that it is customary in the trade to designate as "calcined magnesite" the materials that result from the calcining of magnesite to temperatures that remove the contained carbon dioxide. The finished product, therefore, is not magnesite at all but simply a more or less pure magnesium oxide or magnesia. Furthermore, partly for statistical and partly for commercial reasons, it has been customary, during recent years, to classify as "calcined magnesite" products that result from the heat-treatment of magnesium hydroxide precipitated from magnesium-containing brines; products that, obviously, have no relationship whatever to magnesite. In the listing of magnesia-containing materials, tonnages of which are regularly reported by the Bureau of Mines, reports ordinarily are made under two headings: "caustic calcined" magnesite, in which all of the varieties of products treated at relatively low temperatures are lumped; and "dead-burned" magnesite, in which are included both high-purity and low-purity, and particularly both high-iron and low-iron, materials that have been so heat-treated that the magnesium oxide occurs predominantly as crystalline periclase-materials used almost entirely for refractory purposes. In 1940 the apparent domestic consumption of "caustic calcined" magnesite was approximately 17,000 tons, about 95 per cent of which was produced in this country. The apparent consumption of "dead-burned" magnesite was approximately 172,000 tons, some 82 per cent of which was domestically produced. In both total quantity and percentage of material produced within the United States, these figures are record highs for many years past. UTILIZATION As indicated by these figures, the major tonnage outlet for magnesia is the refractories industry, in which magnesia is employed principally in three ways: (I) as dead-burned grain magnesite for the construction and maintenance of the hearths or bottoms of basic open-hearth furnaces; (2) in the form of refractory magnesite bricks and shapes; and (3) as a chemical

Jan 1, 1942

By J. F. Butler

The degree and type of carbide dispersion resulting from changes in the cooling rate from austenite determine the amount of carbon remaining in solution after slow cooling- from a subsequent subcritical annealing treatment. A difjusion model has been proposecl to explain the effect of carbide dispersion on the amount of carbon retained in solution and the amount of carbon in solution has been related to the degree of carbon strain aging. COTTRELL and Leak&apos; have shown that the rate of strain aging in low-carbon steels is dependent upon the amount of carbon and nitrogen in solution. Carbon can be effectively removed from solution as Fe , C by quench aging at temperatures of 200" C or lower; however, the relatively higher solubility of nitrogen at these temperatures prevents sufficient removal of nitrogen as iron nitrides. For this reason, nitrogen in solution has been considered the major cause of strain aging in rimming grades of commercial low-carbon steels. Nitrogen can be effectively removed from solution and nonaging steel produced through the addition of aluminum to form the stable nitride, AlN; however, the aluminum also causes deoxidation resulting in a killed steel. III an attempt to produce a rimmed steel which was also nonaging, Morgan and Shyne 2 investigated tile strain-aging properties of low-carban steels containing boron and found that strain aging was suplx-essed in steels containing as little as 0.007 pet B. The original purpose of this investigation was to determine the mechanism of strain-aging suppression by boron. Early in the study, the function of boron was discovered to be much like that of aluminum in that the formation of a nitride, BN, removed the nitrogen from solution.&apos; However, during the course of the investigation, an effect of heat treatment upon the strain-aging properties and the amount of carbon in solution was found which could be related to the microstructure of the steel. The purpose of this paper is to examine these relationships among heat treatment, microstructure, carbon in solution, and strain aging in steels where nondetectable amounts of nitrogen are present in solution. EXPERIMENTAL PROCEDURE The investigation was carried out using 0.030 in. by 12. in wire specimens which had been cold swaged and drawn to the final diameter. Table I lists the compositions of the low-carbon steels used. Those with &apos;V&apos; designations were vacuum melted and cast; the alloys designated &apos;AISI&apos; were prepared from high-purity iron obtained from the American

Jan 1, 1962

Jan 1, 1938

Jan 1, 1938

By A. F. Taggart

THE following notes represent significant excerpts from a mass of records of experimental work done in the ore-dressing laboratory at the Columbia School of Mines during the years 1926 to 1928-inclusive. CLASSIFICATION OF EXPERIMENTAL WORK The experiments performed may be grouped for purposes of description under the following general -headings: I. Collecting agents. a. A method for quantifying collecting effect. b. Coating with undissolved collecting agents (oils) c. Action of dissolved collecting agents. II. Frothing agents. a. A method for quantifying frothing effect. b. Relation between frothing effect and chemical composition. III. Inorganic reagents. a. Methods of studying the effects of these reagents. b. Effect on slime dispersion. c. Effect on sulfides. SUMMARY OF THE ORIGINS OF PRESENT-DAY FLOTATION PRACTICE The first practicable, foolproof method of froth flotation was described in U. S. patent 835120, issued in 1906 to Sulman, Picard and Ballot, and in the equivalent patents in other countries. A number of less simple methods of producing the same result had been described previously in patent publications and otherwise.1 The reagents specified in all of these early patents were "oils" and, in addition, some inorganic substance, usually an acid. The quantities of reagents recommended and added were enormous when&apos; compared with those used today.

Jan 1, 1929

By L. G. Huntley

Discussion of the paper of L. G. HUNTLEY,. presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 102, June, 1915, pp. 1333 to 1349. E. W. SHAW, Washington, D. C. (communication to the Secretary*). -The comparatively great extent and uniform character of the Dakota sandstone make it of great interest to the student of rock pores and the movements of their fluid contents. However, compared with other sands in areas of carbonaceous rocks facts concerning it do not seem to be of such great direct importance to the producer for it has thus far yielded few important pools of oil or gas. Information concerning the sandstone is extensive but scattered, hence a general treatise regarding it-particularly its pores, the fluids they contain, and the movements of the fluids-has been much needed. I therefore feel that the. chief thing to be ,desired concerning Mr. Huntley&apos;s paper is that it were more extended, particularly as to the discussion of the data presented. The general structure map of the Dakota is of especial interest. Slight changes in wording seem to be desirable here and there in the paper. For example, at the beginning of the third paragraph one-wonders if flora instead of fauna were not intended. In Figs. 2, 3, 4, and 5 the vertical scale seems incorrect. Concerning the analyses of oil quoted it is noted that they "are given, as indicating what may be expected in different localities." This seems to need modification for the average analysis of oil from Powder River, which indicates for example that this oil begins to boil at 213°C. The fact is that the samples to which this figure refers were taken from seeps long exposed. to the air :find hence the underground Dakota oil of this district no doubt differs profoundly from that which the analysis indicates. The product of a well here would probably differ more in boiling point and other. respects from the samples analyzed than it would from almost any other petroleum in the world. The use of the word synclinorium does not conform to the original definition, but this may be pardonable because misuse of the term, though a different misuse, has become general. Synclinorium is an orographic term and cannot be correctly applied outside of mountain regions, for it is derived in part from the Greek word for mountain. It has, however, been widely used in a purely structural sense for compound syncline. The broad shallow syncline of the Dakota sandstone falls in neither category. Objection might also be made to the use of

Jan 12, 1915

By L. D. Jaffe, R. K. Pitler

IT would clearly be advantageous to produce molten titanium, suitable for alloying and casting, directly from the relatively inexpensive tetra-chloride, without using a metallic reducing agent. Accordingly, a preliminary investigation has been made of the production of titanium by hydrogen reduction of the tetrachloride in an electric arc furnace. For the reaction: TiCl4(g) + 2H2(g) ? Ti(s) + 4HCl(g), Lockhart and his colleagues&apos; have calculated equilibrium constants at 800" to 1500°K, based on tables of Brewer.&apos; Extrapolating these data on the assumption that the heat of reaction varies linearly with temperature, and using Brewer&apos;s value for the heat of fusion, there is obtained for the reaction: TiCl4(g) + 2H2(g) ? Ti(l) + 4HCl(g) an equilibrium constant at 2100°K (100" above the melting point) Kp = (PHCl)4/pTlcl4 (Ph2)2 = 0.167 atm. If this is correct, starting with hydrogen saturated with TiC14 at 25°C, where the vapor pressure of the latter3 is 12.6 mm, and maintaining the overall pressure at 1 atm, 99 1/4 pct of the TiC14 would be reduced to Ti at equilibrium. An arc furnace designed for the melting of titanium and lined with water-cooled copper was used for the preliminary experimental check. Its inside diameter was 2 7/16 in. and height 6 in. The water-cooled electrode was tipped with 3/4 in. diam tung-sten. In the one run carried out, the furnace was charged with a starting batch of 293.35 g of scrap titanium,&apos; analyzing 99.24 pct Ti. After the system was twice pumped out and flushed with argon to remove air, the arc was struck in argon and kept at 400 amp dc, electrode negative, for 1 min to melt the starting batch. Commercial tank hydrogen, dried by passing over silica gel and bubbled through technical grade TiC14 at room temperature, was then admitted to the furnace. The inlet tube directed this gas downward toward the arc and melt; the gas outlet was at the top of the furnace. The quantity of gas passed through was not measured accurately but is estimated to be about 50 liters per min at a few mm of mercury above atmospheric pressure. The arc was held in the H2-TiC14 mixture at 400 amp with little difficulty. After 10 min the arc burned through the copper lining above the melt, admitting water and ending the run. (This had happened frequently in straight melting runs under argon, and is not thought due to the atmosphere used.) In the furnace were found an ingot, several small pieces, and a little metallic powder, evidently formed when water entered the hot furnace. Some titanium also clung to the electrode. The portions were weighed and separately analyzed for titanium. Their total weight was 321.76 g of 94.82 pct overall purity. Much of the impurity consisted of tungsten broken off when the titanium was removed from the electrode. No detailed impurity analysis was made because the starting materials were impure and flooding the furnace introduced further contamination. Thus, the metal recovered contained 305.08 g Ti, as compared to 291.12 g in the starting batch. Titanium could not have been carried over from previous melting runs in the furnace, as the interior was sandblasted and the electrode ground clean before the run. Evidently at least 13.96 g of Ti were produced from TiCl4. Since this would require complete reduction of 430 liters of TiCl, gas at 12.6 mm of Hg, the efficiency of the process must have been rather high. Experimental work is continuing. No reason is seen why the process could not be scaled up to the size of a 30-ton steel-melting arc furnace. In a large unit there would be a large molten pool from which liquid metal could be withdrawn for alloying and casting. The problems of electrodes and power supply are similar to those arising in arc furnaces for melting titanium. Unreacted TiC14 and the HC1 in the exhaust gases could be recovered; unreacted H2 could be dried and re-used. The melt would be saturated with hydrogen, whose solubility in liquid titanium is unknown. Small amounts of hydrogen seem to have little effect on the properties of titanium.5 If the amount introduced was so large as to impair properties or cause casting difficulties, it could be reduced by holding the melt under an inert gas or by pumping on it, prior to casting. Acknowledgment The authors would like to thank I. Preble and M. Goldman for their valuable aid in the experimental work and the thermodynamic calculations, respectively. References 1R. J. Lockhart, J. J. Ward, M. J. Hussey, and J. W. Clegg: In unpublished report, "U. S. Air Force Project Rand. Titanium and Titanium Base Alloys." Battelle Memorial Institute (1949) 37-44. 2 L. Brewer et al: Chemistry and Metallurgy of Miscellaneous Materials—Thermodynamics. Ed. by L. L. Quill. pp 13-39, 60-192. (1950). McGraw-Hill Book Co. 3 K. Arii: Scientific Reports. Tohoku Imp. Univ. (1933) 22, 182. 4 R. S. Dean, J. R. Long, F. S. Wartman, and E. L. Anderson: Transactions AIME (1946) 166, 369-381; Metals Technology (Feb. 1946) TP 1961E. * R. I. Jaffee and I. E. Campbell: Transactions AIME (1949) 185, 646-654; Journal of Metals (Sept. 1949) TP 26813.

Jan 1, 1951

By J. O. Nomland

DuRing the year 1939 the program of the California Arabian Standard Oil Co. in eastern Saudi Arabia consisted of drilling wells to increase the production of Dammam Dome. (This structure is also sometimes referred to as Dhahran Dome.) In addition, in other areas of the concession, wildcat wells are being drilled on geologically favorable structures. In the early wells drilled at Dhahran, production was at a depth of 2000 to 2200 ft. Since discovery of the "Arab zone" below 4300 ft., all of the later wells have been drilled to the deeper productive members. At present there are at Dhahran fivc wells in various stages of drilling or completion. In addition, 15 wells previously were drilled to the upper or lower zones. Although some of the early locations are exceptions, in general the spacing of the wells is at 3000 feet. Prospect testing consisted in drilling one well at Abu Hadriya and one at Ma&apos;agala, about 100 miles northwest and 120 miles west of Dhahran. The first had attained a depth of 8655 ft. without encountering the main Darnmam productive zone, while the second was at a depth of 1372 ft. Both of these wildcat wells are on large dome structures. Production.—During the year 3,933,903 bbl. of approximately 35" gravity oil was produced, all from flowing wells. A part of this production was shipped in barges to the refinery at Bahrein. In early May a 40-mile 10-in. pipe line was completed to the deep-water terminal at Ras Tanura. The ceremony of first opening the valve for flow of oil into an ocean tanker was performed by King Abdulaziz Ibn Saud. Since that time tanker shipments have continued, both to Bahrein and to world markets. Only sufficient gas for camp purposes has been produced. Equipment.—A stabilization plant has been completed at Dhahran and plans have been made for a refinery at Ras Tanura. A modern camp is being built including power plant, central air-conditioning plant, radio station, employees&apos; club and housing facilities for both married and single employees. Both the offices and dwellings are being air-conditioned. There is a hospital, with medical staff and nurses, providing facilities for both Saudi Arabs and Americans.

Jan 1, 1940

By J. O. Nomland

DuRing the year 1939 the program of the California Arabian Standard Oil Co. in eastern Saudi Arabia consisted of drilling wells to increase the production of Dammam Dome. (This structure is also sometimes referred to as Dhahran Dome.) In addition, in other areas of the concession, wildcat wells are being drilled on geologically favorable structures. In the early wells drilled at Dhahran, production was at a depth of 2000 to 2200 ft. Since discovery of the "Arab zone" below 4300 ft., all of the later wells have been drilled to the deeper productive members. At present there are at Dhahran fivc wells in various stages of drilling or completion. In addition, 15 wells previously were drilled to the upper or lower zones. Although some of the early locations are exceptions, in general the spacing of the wells is at 3000 feet. Prospect testing consisted in drilling one well at Abu Hadriya and one at Ma&apos;agala, about 100 miles northwest and 120 miles west of Dhahran. The first had attained a depth of 8655 ft. without encountering the main Darnmam productive zone, while the second was at a depth of 1372 ft. Both of these wildcat wells are on large dome structures. Production.—During the year 3,933,903 bbl. of approximately 35" gravity oil was produced, all from flowing wells. A part of this production was shipped in barges to the refinery at Bahrein. In early May a 40-mile 10-in. pipe line was completed to the deep-water terminal at Ras Tanura. The ceremony of first opening the valve for flow of oil into an ocean tanker was performed by King Abdulaziz Ibn Saud. Since that time tanker shipments have continued, both to Bahrein and to world markets. Only sufficient gas for camp purposes has been produced. Equipment.—A stabilization plant has been completed at Dhahran and plans have been made for a refinery at Ras Tanura. A modern camp is being built including power plant, central air-conditioning plant, radio station, employees&apos; club and housing facilities for both married and single employees. Both the offices and dwellings are being air-conditioned. There is a hospital, with medical staff and nurses, providing facilities for both Saudi Arabs and Americans.

Jan 1, 1940

By George M. Fowler

EVERY year it becomes more difficult to find new mining districts and new ore deposits. Nearly all of the important discoveries so far can be attributed to surface manifestations overlying the ore deposit. In the future greater skill will be necessary to find ore deposits that give little or no indication of their presence. Mining geology is making progress by broadening its attack upon mineralized regions, by including in its investigations studies of the relation of physical-chemical processes to ore precipitation and various phenomena that heretofore have not always been looked upon as major factors in the problems. Such, for example, are petrographic peculiarities that will help determine structure, aspects of strata or formations favorable or unfavorable to structural deformation or mineralization, and renewed studies of chert and dolomite. This broadening attack is not necessarily being directed to the study of large areas, but rather by doing extremely detailed work in three dimensions in relatively small critical areas to find the key to the structure, reasons for the manner of rock deformation, composition and texture of the rock, and other con¬trolling factors in the larger areas.

Jan 1, 1935

By J. E. Johnson

THE production of metal-working tools has been revolutionized within the last 18 years, since the invention by Taylor and White of a process of heat-treating steel tools, which resulted in increasing their cutting capacity several fold over what it had been before. This was an exceedingly important invention, although it consisted principally, in establishing this fact overheating when it accidentally, occurred in the ordinary:-process of forging, spoiled the steel, but if carried very much farther or to-a point that would have been considered absolutely ruinous to the steel under the old ideas, it resulted in imparting a cutting power several times as: high as had ever been obtainable before. The quality that gives the steel this power eventually received the name of "red hardness." This name originated in the fact that tools possessing this property retain their resistance to deformation even when subjected to, such severe cutting stresses that the metal just back of the point is heated, under certain conditions, to a visible red. It is interesting in this connection to note that the edge of the tool itself does not become red because it is continually cooled by the fresh metal into which it is forced. The result of Taylor and White&apos;s invention was an intensive study, of tool steels all over the world and, although there was-great diversity of analysis in the high-speed steels of the early days, these steels today generally have an approximately similar composition, the principal constituents being froth 15 to 20 per cent. of tungsten, from 4 to 6 percent. of chromium, from 1 to 2 per cent. of vanadium, and from 0.50 to 1 per cent. of carbon. It is probably safe to say that standard brands of such high-speed steels will do from five to ten times as much work in a given time as the carbon steels, and even the Musket steels, which were the sole dependence up to the beginning of this century, when the Taylor-White process was discovered. With the increasing cost of labor, it is not surprising that these steels have driven froth the market, for all but limited purposes, the older types of steel.

Jan 2, 1919