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By C. Baldwin Sawyer

J. S. Vanick,* Washington, D. C. (written discussion).—To those who have been confronted with the study of the gas-metal reactions, this paper is a most welcome contribution. My personal interest in work bearing upon this general problem, stimulated by an appreciation of the difficulties inherent to problems of this type, prompts a few words of discussion. Table 2 of the paper shows a gradual increase in the nitrogen content with an increase in pressure, and an interpretation follows in which nitrogcn is used as the compressed medium when the conditions admit that cyanogen gas could be active as a contaminating ingredient. Fusions of electrolytic iron made in the induction furnace in an atmosphere of deoxidized nitrogen and out of contact with contaminating materials have shown no microscopic evidence of -a nitrogen increase; using a refractory-lined graphite crucible in the furnace under the same conditions or admitting air often resulted in the occurrence of nitride needles in the solidified melt. These results suggested that a nitrogenous compound served as a vehicle for the introduction of nitrogen and that such compound was not available when the pure gas and carbon-free refractory were used. The fusion of pure iron in pure nitrogen is perhaps a matter of theoretical interest. The author's work serves a more practical purpose when applied to steels rather than iron. Table 2 reports the absence of nitride needles in melts made under pressure of one atmosphere, although the quantity of nitrogen present would seem to exceed microscopically detectable percentages. In some recent work29 on carburized iron, nitride needles have been observed in areas analyzing as low as 0.015 per cent. nitrogen. This low percentage of nitrogen would indicate that the solubility limit is less than 0.030 per cent. for hypoeutectoid steels. There is the possibility that the areas of pearlite which exist in a hypoeutectoid steel restrict the distribution of nitrogen and limit its presence to the ferritie fields. In view of this work and the references quoted by the author, I am led to expect that the value for the solubility of nitrogen in solidified iron may approach

Jan 1, 1924

By W. C. Leslie

W. C. Leslie (Edgar C. Bain Laboratory for Funda mental Research)—This investigation, with its com bination of high-purity metal, calorimetry, and metallography, will serve as a model for annealing studies for a long time to come. The evidence for a competition between recovery and recrystalliza-tion is particularly convincing. The demonstration of edge-nucleated recrystallization was so clear that it may obscure the necessity for other types of "nucleation" sites; otherwise, single crystals of aluminum could not be recrystallized after cold work. At least three types of sites have been found to operate in iron: 1) high-angle boundaries, probably in the same manner as in aluminum, 2) matrix sites, 3) inclusions or second-phase particles. In each instance, the cells developed during cold work and perfected during recovery are the "nucle for recrystallization. Observations by ourselves and others of the dislocation structure of cold-worked metals and of the structural changes that occur during annealing have led us to doubt the validity of the basic assumption of the Lucke-Detert theory, and of the modification developed by Gordon and Vandermeer, that during recrystallization of a metal containing foreign elements in solid solution a high-angle boundary is ad vancing into a cold-worked matrix having a random distribution of solute atoms. We contend that an es sential part of the cold-working and annealing of solid solution alloys is the trapping of solute atoms by the low-energy "wells" afforded by individual dislocations and by dislocation arrays. If cells are formed during cold work, the cell walls are stabilized by this concentration of solute atoms. Thus, solutes inhibit recrystallization not only by decreas-ing the rate of high-angle boundary migration, but also by preventing the formation of high-angle boundaries by subgrain growth or coalescence, i.e., solutes can inhibit both "nucleation" and growth. In addition to stabilizing the dislocation Structure, the solute-dislocation interactions may produce clusters of solute atoms which are not as readily assimilated into the recrystallized grains as are individual solute atoms. There is an additional complication. The dislocation structure formed upon cold working a dilute solid solution may not be the same as that formed during cold working of the pure solvent metal. The solute can either enhance or minimize the formation of cells during cold working. Both effects have been observed in binary alloys of iron. The annealing process is inextricably connected with the mechanisms of strain hardening and solid solution hardening. Although the correlation between experimental boundary migration rates and the predictions made from the theoretical equations are impressive, it should be mentioned that in at least four other instances (Pb-Ag and pb-Au,15, Fe-Mn,16, Fe-Mo)17 the agreement was rather poor. In brief, while it is probable that the migration of high-angle boundaries is held back by solutes in the manner described, this is only a partial explanation of the total effect of solutes upon recrystallization of cold-worked alloys. Paul Gordon and R. A. Vandermeer (author's reply)— The authors first wish to thank Dr. Leslie for his compliments of this work. It is perhaps worth pointing out that some of Dr. Leslie's remarks are directed toward subject matter covered in two earlier papers in our work.18,19 We agree with Dr. Leslie's main contention that the exact nature of the metal structure in the vicinity of a boundary should have an effect on the boundary migration. The theory of Lucke and Detert does not take such detail into account, nor does it account for orientation effects on the migration rates. We assume that since our data checks the theory so well, the effects of detailed structure are statistically averaged out by the polycrystalline techniques used just as are the effects of orientation factors.

Jan 1, 1963

By R. U. Fitting, A. C. Bulnes

Field experience with limestone and sandstone production indicates the existence of wide differences between the reservoir behavior of these two types of formation. Little attention appears to have been given to the separate study of the flow of fluids and the retention of fluids in limestones. This paper presents data and arguments to demonstrate the existence of a difference between the two types of formation, and urges the separate intensive investigation of limestone reservoirs. AH experimental data presented pertain to dolomitic limestone formations in west Texas and New Mexico. Two kinds of Porous media are recognized— intergranular and intermediate. Intergranular rocks are those in which the porosity and permeability are determined by the geometrical properties and the sorting of the sedimentary units; intermediate rocks, those in which there is no direct relationship between grain properties and the porosity and permeability. Limestones in general are intermediate media. The partial relationship between porosity and permeability of any class of Porous media is represelried by an area of .finite extent and definite shape on the permeability-porosity plane. The horizontal and vertical variations of porosity and of permeability in limestone and sandstone formations are discussed and compared. Comparisons are made of connate-water content, the relative permeability-saturation relationship, and capillary phenomena in the two kinds of rocks. A number of tentative conclusions are drawn relative to the reservoir properties of lime- stones; in particular, (I) dolomitic limestones are oil bearing and apparently are oil productive in zones of permeability less than 0.1 millidarcyj and (2) primary depletion (by gas expansion) oil saturations may be lower in dolomitic limestones than in sandstones. Introduction It is well known that the reservoir performance of limestones displays numerous irregularities when compared with that of sandstones, and that the departures from "normal" behavior of limestones are more frequent and generally more marked than in sandstones. This is particularly true of fractured limestones and those that have undergone considerable development of secondary porosity' A review of the literature of production research published during the past 15 years reveals a startling absence of theoretical and experimental investigations directed specifically toward explaining and predicting the performance of limestone reservoirs, even. though such problems as the prediction of water encroachment and the estimation of ultimate recoveries continue at the "inspired guess" stage. By far the greater part of the experimental data reported pertain to measurements on sandstone core samples, while the theoretical studies, almost without exception, are developed from the assumption of an ideal porous medium and therefore seldom are applicable to limestone formations. The chief cause of this situation appears to be the common belief that, to all practical intents and purposes, sandstones and the majority of producing limestone formations

Jan 1, 1945

By M. H. Richman, W. D. Sproul

THE indexing of a field-ion micrograph is in many cases similar to the indexing of the poles of a stereo-graphic projection.* If one has a standard projection as a guide, the task of indexing is relatively simple. In this way, field-ion micrographs of bcc and fcc wires have been oriented from projections available in most any text on X-ray diffraction. These books always illustrate the projections for the bcc and fcc structures and even for a particular hcp structure. There is no "standard" hcp projection because the angles between planes depend on the c/o ratio of the unit cell. In order to index field-ion micrographs of hcp metals, one must compute the angles between various planes—a rather laborious task. In recent work,, we have had to identify the structure and index the orientation of field-ion micrographs of the compounds WC and W,C. To overcome the problem of computing angles by hand or calculator, a program was written in Fortran lV for use on the IBM 360, Model 50 which will compute all angles between planeswith indices (hlklll) and (17,k,l2) in the range from (447) to (444) for any given c/o ratio. The program, which is more specific than that of Camp and clum, was so written as to take advantage of the multiplicity of the hexagonal system, and, for the limits defined above, only 26,649 values out of a possible 265,721 values had to be computed. This is a 90 pct saving in time (and cost) and was accomplished in the following way. Because the lattice parameters of the hexagonal crystal system are defined such that: a = b * c [1] the I index does not enter into the multiplicity (i.e., it cannot be transposed with the h or k indices), and all possible values of h and I, from 4 to 4 must be used—a total of eighty-one combinations. The index h2 varies the most—it must assume values from - Ill,: to 3Ihl. The indices kl and k2 are always equal and vary

Jan 1, 1969

By G. Sachs, B. B. Muvdi, E. P. Klier

IT is now generally i-ecognized that hydrogen is responsible for delayed failures encountered in high-strength steels,'.' and the hydrogen responsible for the embrittlement is introduced in the cathodic cleaning and plating operations to which these steels are subjected. Numerous test methods have been used in the past for the determination of brittleness in embrittled parts, namely tension? = notch-tension:' impact,' stress-rupture: a and bend tests.% * Several of these tests are not suitable for routine testing.

Jan 1, 1958

By George Burgess

I. INTRODUCTION THE suggestion has often been made that it would be highly desirable, at least for certain grades of steel, to be able to control more certainly, by pyrometric measurement or otherwise, the temperatures of the operation of the open-hearth and other furnaces used in the manufacture of steel and iron. That the properties of the ingot and finally of the finished steel product are intimately related to the final temperatures attained by-the metal inn the furnace and to the temperature of casting, has been recognized by metallurgists for a long time, and this question has been very thoroughly treated, especially by Prof. Henry M. Howe, and by A. W. and H. Brearley.1 It is the object of this paper to demonstrate that in so war as casting temperatures of furnaces, steel ingots, and similar operations involving the temperatures of streams of iron and steel are concerned, well-known pyrometric methods s may be easily applied-if certain recently determined corrections are made and precautions taken-with a relatively high degree of accuracy. Greater but not insurmountable difficulties will be encountered in. the case of open-hearth furnace temperatures, while for" those of the converter type a ready solution does not seem practicable. It appears that certain essential data have always been lacking in reporting observations such as those of Le Chatelier in 1892. Thus the correction to be applied for the characteristic radiation-or emissivity¬has hitherto not been adequately taken into account nor the limitations of the several possible pyrometric methods clearly recognized.

Jan 2, 1917

By Bernard MacDonald

The writing of this paper was prompted by the discussion by H. M. Chance of the paper written by Thomas M. Chance,l and by the remarks of the editor in which he stated that while the matter contained in discussion did not refer to the original paper it " was presented as of interest to the operators of cyanide and other lixiviation processes dealing with fluid mixtures of varying specific gravity." For some years past the principle enunciated in the discussion referred to has been known to the writer and demonstrated by him to be an efficient and economical way of separating water or solution from solids in the cyanidation, lixiviation or acid leaching of ore pulps. In utilizing this principle in commercial practice he has invented a method whereby not only the separation of solution from solids may be effected in any given tank, but also the counter migration of the solids and solution may be effected continuously through a series of tanks in which the hydro-metallurgical treatment of ore pulps is being carried on. In effect this method is analogous to the counter-current system, but is different physically in that it is carried on throughout a series of tanks on practically the same level, continuously and automatically, by hydrostatic pressure and gravity-flow, without the aid of intervening pumps or elevators, at the same time that agitation is being carried on in the same tanks. In the Parral system, agitation is effected in tanks by a number of air lifts of comparatively small diameter through which the pulp is continuously transferred from the bottom of the tank and spouted horizontally on top of the charge. The spouting force of the several streams thus discharged maintains a rotary flow in the pulp charge which extends from top to bottom of the tank. This continuous transfer of pulp and the spiral flow from top to bottom of the tank maintains the pulp constituents in uniform proportions and meets the requirements of efficient treatment in a most economical manner. The quantity of compressed air required is very small, as the pulp is not lifted but simply transferred from the bottom to the top of the tank charge under hydrostatic balance. Fig. 1 gives a bird's-eye view of two adjoining tanks in any series equipped with the apparatus for producing the separation of

Jan 1, 1919

By William Y. Holland, Roger M. Cook

In view of the increasingly widespread deterioration of concrete structures as the result of the interaction of the alkalies sodium and potassium released by hydration of portland cement and susceptible rocks and minerals in aggregates, it is believed that a paper summarizing the geographic distribution of these aggregates will be of interest to producers and users of concrete, concrete products, and concrete-making materials. THIS paper reviews the problem of alkali-aggre-gate reaction in concrete and describes the geologic and geographic occurrence and distribution of alkali-reactive sand and gravel in western United States. It includes no discussion of crushed stone or synthetic aggregates. Most deposits of sand and gravel are accumulations of particles of rocks and minerals from a variety of sources, and it is not unusual for at least one or two varieties of the rocks to contain some form of reactive material. Examination by petro-graphic methods of many sands and gravels, as well as manufactured aggregates, has shown that a comparatively high proportion of the deposits does contain, in greater or lesser degree, rocks and minerals known to be deleteriously reactive with the alkalies of cement. Fortunately the amount of reactive materials is commonly less than that necessary to cause deleterious effects in concrete. As investigation of unsound concrete structures progresses, it becomes evident that the alkali-aggre-gate reaction is even more widespread than supposed, Figs. 1 and 2. Even though some parts of the country appear at present to be immune, further investigations will probably show that the effects of alkali-aggregate reaction can be seen in many structures in these areas, although only on a small scale in most of them. Many concrete structures will, of course, have lived their useful life before disintegration from this cause is serious, and in others the alkali-aggregate reaction may never become significant even though the microscopic evidence of reaction is present. The alkali-aggregate reaction first was reported to be a cause of deterioration of concrete in 1940 when Stanton1 described expansion of concrete pavements in California. Similar expansion and deterioration of concrete was recognized during succeeding years in concrete structures located in many parts of the country, but particularly in the western states. A number of concrete laboratories2 became interested in the problem. It was soon determined that only certain combinations of aggregate and cement caused the alkali-aggregate reaction to take place, and moreover that the reaction progresses only in the presence of water. Further research proved that cements containing more than 0.60 pct total alkalies (pct Na,O + 0.658 x pct K2O), when used with aggregates containing appreciable amounts of reactive ingredients, caused the reaction to take place, usually with subsequent deterioration of the concrete. During the last few years this limitation has been adhered to in both government and private construction as the maximum allowable alkali content of cement to be used with aggregates of known alkali reactivity. Because of this limitation, it appears that deleterious reaction either has been reduced or eliminated in many recently built structures in which it probably would otherwise have occurred. Recent tests have shown that the degree of expansion obtained with any particular cement-aggre-gate combination depends not only on the alkali content of the cement but also upon the relation of this alkali content to the amount and degree of reactivity of reactive constituents in the aggregate.' In laboratory mortar bars, opal and cements with alkali content of as low as 0.2 pct (as equivalent of Na2O) have produced deleterious expansion as the result of alkali-aggregate reaction. These experiments demonstrate that aggregates containing even 0.1 pct of opal are deleteriously reactive. It was soon determined that alkali-silica gels were formed by the interaction of the alkalies of the cement and the reactive aggregate, Figs. 3 and 4. Osmotic or swelling pressures produced by the continued hydration of these gels cause expansion of the concrete with resulting cracking, warping, and dislocation. Evidence of the alkali-aggregate reaction can be seen by a petrographic study of the deteriorated concrete. Among the first structures studied by this method was Parker Dam on the Colorado River, California-Arizona. In the concrete from this dam pebbles of rhyolite, andesite, siliceous limestone, and chalcedonic chert were found to be reactive.

Jan 1, 1954

By T. J. Koppenaal, M. E. Fine

The critical resolved shear stress of aCu-A1 single crystals has been investigated as a function of composition, testing temperature, and strain rate. The strength, and its temperature and strain rate dependency increase markedly with aluminum content. The solid solution strengthening at 4.2°K is much larger than at room temperature. The activation energy for the low temperature dislocation cutting process increases from about 0.17 ev for a 0.5 at. pct A1 alloy to about 0.50 ev for a 14 at. pct A1 alloy. This result is attributed to an increase in the width of extended dislocations due to the known decrease in the stacking fault energy. In addition, the activation volumes at 4.2 and 77°K decrease with aluminum additions. Concerning the solid solution strengthening in the 296° to 373°K range, no definite conclusions are reached, but it is suggested that subgrains and cutting of subgrains are important. In a previous paper,' the authors reported that adding aluminum to copper produces two types of strengthening: a yield point effect and an increase in the lower yield stress. This behavior is illustrated in Fig. 1 by shear stress-shear strain curves of furnace-cooled single crystals of pure copper and Cu-14 at. pct A1. The yield point effect, At, was thoroughly studied previously1 and shown to be associated with short-range order. The present paper reports an investigation of the lower-yield stress in aCu-A1 single crystals as a function of composition, testing temperature, and strain rate. EXPERIMENTAL PROCEDURE Single cryski1 tensile specimens were prepared in the same manner as previously described.l Briefly,

Jan 1, 1962

By Shiro Ban-ya, John Chipman

Using the same experimental method previously described, the activity of sulfur in a number of quaternary and more complex liquid iron alloys at 1550oC is determined. A "cross-product term zj.zk is determined for each of the quaternary alloys to take account of the mutual effects of the combinalion on the indi-vidual contributions to In 5 The interactiotl coefjicienls delermined for ternary solutions and cross-pvoducl coefficierlts from the quaternary systems are used to estimate the activity coefficient of sulfur in more complex alloys. OUR recent papers 1,2 have described new determinations of the activity of sulfur in Fe-S binary and Fe-S-j ternary solutions, but the practical applications of these data require the estimation of activity of sulfur in more complex systems. Previously, Sherman and chipman3 devised an approximate method for calculating the activity of sulfur in complex systems by summing the contributions to the logarithm of the activity coefficient of each element in the alloy. This procedure is more successful, as one of us has pointed out,4 when the concentration variable is taken as zs = ns/(nFe — nS t CLJ~ nj) rather than the conventional atom fraction x~ = nS/(nF, + nS + Enj). In the former definition, which is based on analogy to interstitial solutions, the value assigned to uj is normally +1 for metallic and -1 for nonmetallic elements." In addition, however, the effects of mutual interaction between alloying elements must be considered for the accurate estimation of the activity of sulfur in more complex systems. The purpose of this investigation has been to devise a more reliable method for estimating the activity coefficient of sulfur in nmIticomponent iron alloys. The measurements were carried out on some quaternary systems Fe-S-j-k for combinations of silicon, chromium, nickel, cobalt, molybdenum, and tungsten. Manganese was not included since the experimental method has been found unsatisfactory for volatile, sulfide-forming elements. The experimental method was the same in every detail as described previously. 1,2 The concentrations of sulfur, silicon, chromium, and copper in the quenched metals were determined by chemical analysis but those of nickel, cobalt, molybdenum, and tungsten were calculated from charged amounts. Iron sulfide was included in the charges in amounts estimated to furnish approximately the final sulfur content. CALCULATION W2 have shown2 that when zs and zj are the concentration variables in a ternary Fe-S-j solution the logarithm of the activity coefficient S = a~/zg is a linear function of the variables as and aj defined as follows:

Jan 1, 1970

By Bryon W. Cheever

While working upon the processes which have been descaribed from time to time in the Transactions of the Institute for the estimation of these elements, I discovered that certain reactions take place under certain conditions which if overlooked, give erroneous results. Some of these reactions are new, to me at least. Estimation of Manganese. A weighed sample is dissolved in nitric acid and the manganese precipitated by potassium chlorate in the usual manner, care being taken to add some strong nitric acid at the last, and boil, to completely destroy the chlorate. Filter through purified asbestos, suck the filter dry with an aspirator; then wash with HNO3(1.40sp). gr.) until the acid comes through clear, and again suck dry with the aspirator. The nitric acid used for washing must be free from nitrous acid, for this acid reduces the peroxide of manganese; the lower oxide thus formed is dissolved by the strong nitric acid and is carried through the filter; some manganese also will nearly always be dissolved if the precipitate is washed with water. The nitric

Jan 1, 1886

By D. E. Norquist, J. E. Moeller

The results of wear on marked balls, 4, 31/2, 3, and 2 in. diam are given. All balls were forged steel of practically the same chemical analysis and hardness. The results indicate that balls in a given mill for a given length of time will have equal diameter losses, regardless of size.

Jan 1, 1950

By Clarence M. Haight

The general practice in drill sharpening shops, of which descriptions have been written, is about as follows: The bit is heated to 1600" to 1900°F. Then when forged to the proper shape and size in the sharpening machine, the steel is allowed to cool; it is then passed to a hardening furnace where only the end is heated to about 1450" F., and then quenched in cold water, brine, or in brine with oil on top.

Jan 1, 1922

By F. Lawson, N. A. Sareyed-Dim

A rotating disk of iron precipitant in a high temperature batch reactor has been used to study the kinetics of precipitation of nickel from low concentration aqueous solutions. Under inert atmosphere conditions, for temperatures up to 150°C, the rate of nickel deposition at pH25°C of 5 to 6 is controlled both by the rate at which nickel ions reach the surface and the rate of chemical reaction at the surface. However, the presence of oxygen in the atmosphere above the reacting system increases the nickel deposition rate dramatically. It is suggested that under the experimental conditions used, hydrogen atoms are adsorbed on both the iron and nickel, thus reducing the number of sites available for the cementation reaction. Oxygen acts as a depolarizer for hydrogen.

Jan 1, 1977

By Dewitt T. Ring

Lack of reliable detailed production figures for earlier years, together with the loose nomenclature in reference to producing horizons and the application of the term "field" without any definite meaning or restriction, has made it impossible to gather statistical data suitable for the Institute's form. In common with all other producing areas in the United States, Ohio has felt severely the economic ills of the entire industry during the past year. With overproduction, not only of crude but also of refined products, going on throughout the country, the price structure as a direct consequence has weakened on Ohio oils. Valuable crude is being sold at a big loss today because producers arc willing to, and do, sell more than the market can absorb. The axe hangs heavy over the heads of Ohio producers, and will until something constructive is done to keep supply in proportion to demand. This not only applies to Ohio but to the entire industry. Production of Pennsylvania grade in Ohio was under 50 per cent proration, which has been in effect since Oct. 1, 1937. Three price cuts since February have lowered the posted price from $1.70 to $1.18, a 30 per cent reduction; other grades were less drastically reduced. Pipeline storage facilities were limited; many producers were faced with the problem of providing their own storage or the risk of ruining their wells. If they wanted to pull and abandon wells, there was no market for junk equipment. Many employees have been cut to half time and in a number of instances their services entirely dispensed with. Summary of Production and Drilling Both oil and gas production in the state during 1938 showed a definite decline over the previous year. (A table showing production by years from 1876 through 1937 was published in Vol. 127 of the Transactions.) The total production of crude oil in the state for 1938 was 3,357,914 bbl., as compared with 3,654,000 bbl. in 1937, a decrease of 7.1 per cent. At

Jan 1, 1939

By Dewitt T. Ring

Lack of reliable detailed production figures for earlier years, together with the loose nomenclature in reference to producing horizons and the application of the term "field" without any definite meaning or restriction, has made it impossible to gather statistical data suitable for the Institute's form. In common with all other producing areas in the United States, Ohio has felt severely the economic ills of the entire industry during the past year. With overproduction, not only of crude but also of refined products, going on throughout the country, the price structure as a direct consequence has weakened on Ohio oils. Valuable crude is being sold at a big loss today because producers arc willing to, and do, sell more than the market can absorb. The axe hangs heavy over the heads of Ohio producers, and will until something constructive is done to keep supply in proportion to demand. This not only applies to Ohio but to the entire industry. Production of Pennsylvania grade in Ohio was under 50 per cent proration, which has been in effect since Oct. 1, 1937. Three price cuts since February have lowered the posted price from $1.70 to $1.18, a 30 per cent reduction; other grades were less drastically reduced. Pipeline storage facilities were limited; many producers were faced with the problem of providing their own storage or the risk of ruining their wells. If they wanted to pull and abandon wells, there was no market for junk equipment. Many employees have been cut to half time and in a number of instances their services entirely dispensed with. Summary of Production and Drilling Both oil and gas production in the state during 1938 showed a definite decline over the previous year. (A table showing production by years from 1876 through 1937 was published in Vol. 127 of the Transactions.) The total production of crude oil in the state for 1938 was 3,357,914 bbl., as compared with 3,654,000 bbl. in 1937, a decrease of 7.1 per cent. At

Jan 1, 1939

By John Chipman, Daniel Dutilloy

The equilibrium of gaseolis H2O-H2 mixtures with liquid iron-phosphorus alloys in the range 0 to 3 pct P is used to establish the increuse of the activity coefficient of oxygen, in the presence of phosphorus. Two different sampling techniques are used. THE importance of oxygen as a refining agent in steelmaking operations makes it desirable to improve our understanding of its behavior. Phosphorus which is always present in the ores has adverse effects on steel properties and its removal is necessary. The present study was undertaken to evaluate the interaction of oxygen and phosphorus in molten iron. Bookey, Richardson, and welch1 have studied the phosphorus-oxygen equilibria in liquid iron in the presence of lime. They used a mixture of hydrogen and water vapor to control the oxygen potential and worked with crucibles made of tetracalcium phosphate and lime. At low phosphorus concentration, i.e., at high oxygen, they observed a marked deviation in their results. They tentatively ascribed this to a large negative effect of oxygen on the activity of phosphorus. This was then included by chipman2 in his review of interactions in liquid iron. Pearson and Turkdogan 3 have later reported an interaction parameter They equilibrated a mixture of hydrogen and water vapor with an iron-phosphorus alloy contained in an alumina crucible and sampled the melt by suction in a silica tube. The solubility of oxygen in iron-phosphorus alloys has been studied by Levenets and Samarin.4 They reported an interaction parameter

Jan 1, 1961

By James K. Stanley

IRON-COBALT alloys in the range of 35-50 pct cobalt are of interest in the electrical industry because they possess the highest magnetic saturation of any magnetic material known.1,2 The magnetic saturation induction of the 35 pct alloy is 24,200 gausses, compared to 21,600 for pure iron (Fig I). This difference is significant in electrical apparatus, where weight or space is at a premium. Saturation values higher than that for iron can be attained up to about 70 pct Co but economics restrict the use to as low a cobalt content as possible without sacrifice of saturation. Fig 2 shows the iron-cobalt equilibrium diagram. Up to the present time, two factors have retarded the use of iron-cobalt alloys in the electrical industry for magnetic purposes.† One is the high cost of cobalt ($1.50 per pound) and the other is the inherent brittleness of the binary iron-cobalt alloys. Straight iron-cobalt alloys up to 25 pct cobalt are ductile and easy to process to thin sheet or strip by conventional methods of hot and cold rolling, but the alloys containing higher percentages of cobalt, including those for which the saturation magnetization is a maximum (35 to 40 pct), are increasingly brittle with increasing cobalt, at least up to 50 pct, and are consequently difficult to process, either hot or cold. Work by White and Wah13 indicated that iron-cobalt alloys could be made ductile by alloying with vanadium, and after quenching the alloys (vanadium up to about 4 pct) were found to be cold rollable to very thin gauges. With this as a background, we resumed our work on these alloys with the objective of developing methods for economical commercial production of wide strip. For this purpose we have concentrated on the 35 pct alloy in order to obtain the highest possible saturation value. Experiments were carried out on many alloy additions to the iron-cobalt alloys and on the response of these compositions to heat treatments. This work finally culminated in a commercially producible iron-cobalt alloy which has been named Hiperco. * MATERIALS STUDIED AND PROCEDURE Binary alloys of iron and cobalt in the range of 35 pct cobalt are difficult to hot work (by forging or rolling) without such additions as C, Mn, Si, V, Cr, Mo, W or perhaps others. Another beneficial effect of such additions is that they in-crease to a greater or less extent the strangely low electrical resistivity of these alloys (about 10 microohms per cm3

Jan 1, 1947

By H. W. Miller, V. H. Wilhelm

During 1932 the oil industry persistently endeavored to maintain a rate of production that would permit a profitable price structure. Much effort was concentrated on curtailment of both production and drilling. The tendency in curtailment was to shut in reserves where closely held and not subjected to drainage, and to allow town-lot fields such as Long Beach, Santa Fe Springs, Playa Del Rey and Huntington Beach a greater percentage of allotment. Marginal wells were given special consideration; only a small percentage of curtailment wag required, making their operations profitable. Naturally the decline in production of town-lot fields, under slight curtailment, is very rapid, hence production that is restricted in fields controlled by major interests at the present time will profit considerably in the future, as California reserves do not appear adequate to sustain heavy withdrawals over a long period of time. California production during 1932 was much greater than additions to reserves during the year. The state produced 10,701,238 bbl. of crude oil less in 1932 than in 1931, while total stocks (all petroleum commodities) decreased 1,589,524 bbl. Had all operators kept strictly within their allotted 'production, the total crude production decline would have been approximately 20,000,000 bbl. and total stock decrease 3,000,000 barrels. Estimated proven oil reserves for California were 3,965,000,000 bbl. on Jan. 1, 1932, as compared with 3,784,120,000 bbl. as of Jan. 1, 1933, a decrease of 180,880,000 barrels. Approximately 85 per cent of the 178,127,794 bbl. of oil produced during 1932 was withdrawn from old reserves in settled fields and the remaining 15 per cent from new sources such as Kettleman Hills North Dome, Belridge, San Miguelito and Dominguez deep zone. The oil reserves of Kettleman Hills North Dome are estimated to be approximately 50 per cent of the total oil reserves, of California and they may be drawn upon at a much greater rate than the remainder of the state's oil fields.

Jan 1, 1933

By John Chipman, Minu N. Dastur

This paper presents equilibrium data on the reaction of water vapor with vanadium dissolved in liquid iron at 1600°C. The thermo-dynamic behavior of vanadium and oxygen when present together in the melt is discussed. A deoxidation diagram is presented which shows the concentrations and activities of vanadium and oxygen in equilibrium with V209 or FeV2O4. STUDIES of the chemical behavior of oxygen dissolved in pure liquid iron1-3 have served to determine with a fair degree of accuracy the thermody-namic properties of this binary solution. The practical problems of steelmaking, however, involve not the simple binary but ternary and more complex solutions. Only a beginning has been made toward understanding the behavior of such systems. The silicon-manganese-oxygen relationship was studied long ago by Korber and Oelsen4 and more recently by Hilty and Crafts." The carbon-oxygen reaction was investigated by Vacher and Hamilton6 and by Marshall and Chipman.7 A number of deoxidizing reactions have been studied empirica1lys'10 with the object of determining the appropriate "deoxidation constants." The work of Chen and Chipman" afforded a clear-cut view of the effect of the alloy element, chromium, on the thermodynamic activity of oxygen in liquid ternary solutions. These investigators determined the oxygen content of experimental melts which had been brought into equilibrium with a controlled atmosphere of hydrogen and water vapor and were able to show that the presence of chromium decreases the activity coefficient of oxygen. They determined also the conditions under which the two deoxidation products, Cr2O3 and FeCr2O4, were formed and showed that the activity of residual oxygen is considerably less than its percentage. It was the object of this investigation to apply a similar method to the study of molten alloys of iron, vanadium, and oxygen. Vanadium was once considered a moderately potent deoxidizer, but this is now known to be erroneous, in the light of its behavior in steelmaking practice. Its reaction with oxygen retains a certain amount of practical interest in that a high percentage of one element places a limit on the amount of the other that can be retained. As a deoxidizer it will be shown that vanadium lies between chromium and silicon. Experimental Method The apparatus was that used by the authors3 in their study of the equilibrium in the reaction: H2(g) +O = H2O(g);K,= [1] PII., ao Crucibles of Norton alundum or of pure alumina were used. The latter were made in this laboratory and were of high strength and low porosity. Under conditions of use they imparted no significant amount of aluminum (less than 0.01 pct) to the bath. Temperature measurements were made with the optical equipment and calibration chart of Dastur and Gokcen.= The charge was made up of calculated amounts of ferrovanadium (20 pct V) and clean electrolytic iron totaling approximately 70 g. The first few heats were made in alumina crucibles with an insufficient amount of vanadium so that no oxide of vanadium would be precipitated under the particular gas composition. All the heats were made at 1600 °C under a high preheat and with four parts of argon to one part of hydrogen in the gas mixture to prevent thermal diffusion. The rate of gas flow was maintained constant at 250 to 300 ml per min of hydrogen. The time for each heat was three quarters of an hour after the melt had melted and attained the required temperature (1600°C). The water-vapor content of the entrant gas mixture was gradually raised in succeeding heats, keeping the vanadium content of the melt constant. This was controlled by manipulation of saturator temperature. A point was reached when for a given H2O:H2 ratio some of the dissolved vanadium was oxidized and appeared as a thin, bright oxide film on top of the melt. By raising the temperature of the melt it was possible to dissolve the oxide film which reappeared as soon as it was cooled down to 1600°C. The temperature readings taken on the oxide film were consistently higher by 80" to 85 °C as observed by the optical pyrometer. The heat was allowed to come to equilibrium under a partial covering of this oxide film. At the end of the run the power and preheater were shut off and the crucible containing the melt was lowered down into the cooler region in the furnace. This method of quenching proved quite

Jan 1, 1952