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By H. T. Bowman

FOR more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the 1860's it was recognized that the process would benefit by some type of instrumental control.1 However, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower's eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham3' A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient monoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. CARBON-FEO RELATIONSHIP In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by McCutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a different method than were those

Jan 1, 1942

By M. H. Mueller, P. A. Beck, W. P. Chernock

HARRIS introduced the term inverse pole figure for the diagrams previously used by Barrett' to represent the volume fraction p(a,ß) of material in various orientations with respect to the fiber axis in a specimen with fiber texture. The direction of the fiber axis with respect to the crystal lattice is specified by the two independent angle variables a and ß. In such a diagram p gives the fiber axis density distribution over the various crystallographic directions. The p(a,ß) may be given in a two-dimensional diagram by means of contour lines (p=con-stant) in a stereographic projection. The inverse pole figure incorporates in a single contour line diagram all the information given conventionally in pole charts for various (hkl) reflections and, therefore, it represents a considerable degree of condensation. Also, it gives this information directly in terms of the volume fraction of the specimen in various orientations, and it obviates the necessity of referring back and forth between the various pole charts in an attempt to interpret them in terms of orientations. Inverse pole figures undoubtedly represent the most adequate method for describing a texture in a quantitative manner and, at least in the case of fiber textures, this method is certainly a practicable one. Harris described1 a simple procedure for determining at least the rough outlines of a quantitative inverse pole figure. This method depends on the measurement of the intensity of X-ray reflections from various (hkl) planes lying parallel to the same specimen surface. In the case of a rod, reflections from a plane specimen surface perpendicular to the rod axis (fiber texture axis) are to be used. Harris has shown that the measured intensities I,,, reflected by crystal planes (hkl), aligned perpendicularly to the fiber axis of a specimen with unknown fiber texture, and the corresponding intensity Iu nkl from a random specimen are related to the p(a,ß) value for the unknown texture by the following equation IAkl/I°Aklw=c/c°.p(a, ß) [1] where C and C° re parameters depending on the crystal imperfections (extinction), surface preparation (e.g., thickness of oxide layer), the absorption coefficient in the specimen, effective line breadth, and instrumental factors. The values of the variables a and ß1 defining the crystal orientation, depend only on the indices hkl of the reflecting plane perpendicular to the fiber axis. Since p, as described by Harris1, is normalized in such a way that upon integration over the total orientation range its mean value is 1, the parameter C/C may be calculated approximately by the summation of Eq. l over all available X-ray reflections hkl, corresponding to a set of discrete orientations (rather than by integration over the complete range of orientations represented by the continuous variables a and ß). From the summation of Eq. 1 1/n SI AKL/I° Akl = C/C. SP(a,ß)/n is obtained where, as stated above 2p(a,ß) =1. n Therefore

Jan 1, 1959

By A. W. Gauger

IT is with some trepidation that I approach my subject, for I know that I shall at once incur the suspicion of the mechanical engineer, with his concern for boiler tests and efficiencies; of the mining engineer, with his mechanization problems; and of the chemical engineer with his unit processes. Nevertheless, it must be recognized that the technology of fuels, the systematic body of knowledge relating to the production, processing and utilization of mineral fuels, has grown to such proportions and involves so many widely diverse applications of fundamental science and engineering that it behooves us to stop and consider just what its status is in relation to other technologies, as well as in relation to the present and future needs of the social order. The time has come when technologists, applied scientists and engineers must consider the possible effects that their achievements may have 0n Society. The development of a machine to replace several hundred men is a fine achievement when considered solely from the point of view of creative endeavor. But what of the men who are displaced by the machine! Does not the responsibility for the development of this machine embrace as well the consequences of obsolescence and technological unemployment resulting from such development? I believe that it does and that we must recognize this fact in our practice of engineering and technology as well as in the training of future engineers and technologists. MAGNITUDE OF THE FUELS INDUSTRY Fuel technology is the body of knowledge that relates to the mineral fuels. The fuels industry is by far the most important of all our mineral industries. The chart in Fig. I, reprinted from U. S. Bureau of Mines Information Circular No. 6643, indicates the comparative values of metals, fuels and other nonmetallic minerals for the year 1929. Of the grand total of 13 1/4 billions of dollars in value of minerals at the mines, the mineral fuels contributed 48 per cent. Coal, with 34.4 per cent, exceeded the value of any other single mineral. In fact, the value of the production of the Pennsylvania anthracite mines alone annually exceeds the value of the gold production of the entire world. Petroleum and natural gas in 1020 contributed 14.3 per cent and 3.3 per cent, respectively, of the total value of world mineral production. So much for the world picture; let us now look at the situation in the United States. Over the 60-year period 1880 to 1939, $46,409,727,000 of metallic products, S80,788,852,000 of fuels (coal, petroleum, natural gas, natural gasoline) and $27,871,000,000 of nonmetallic minerals other than fuels were produced. The mineral fuels have contributed 52.7 per cent of the entire mineral wealth produced over this period that has seen such tremendous industrial development in our country. As a matter of fact, our present industrial civilization has been made possible through the use of the

Jan 1, 1942

By Gordon M. Yocom

A PROPER consideration of the subject of this paper should include economic aspects as well as the technical phases of the metallurgy, production, and properties of the product. The metallurgical phases of the processing and properties of the product will be considered only from practical aspects and within the scope of the writer's experience with tonnage production. The Bessemer process was invented 85 years ago and became important because it put steel manufacture upon a larger and less costly basis. In America the Bessemer production has declined for many years and has not maintained its proportionate place with the rapid advances of the open hearth. The achievements in the open-hearth field were attained by the greater number of technical people attracted to that branch of the industry. The antipathy of technical students for the older and less popular Bessemer field gradually weakened the forces defending it and retarded the development of new and better methods. In Europe the economic advantage of the basic Bessemer process has not been overlooked and the tonnage usually is greater than that of the open hearth. The acid process has been the subject of renewed attention in America during the past few years and those who are more familiar with it are striving to show that the method is too valuable to abandon. A considerable tonnage of Bessemer-blown metal, in both molten and ingot forms, used in connection with the open-hearth practice makes it an important auxiliary unit to the industry. This practice aids in modifying the price level of heavy remelting scrap in addition to speeding up the open-hearth operation. The use of Bessemer steel has continued not only because of periodic economic advantages but also because of certain inherent qualities of machinability, weldability and stiffness, which are valuable for many applications. The properties of stiffness and rather high reaction to cold-work require some modification in order to meet the demands of modern methods of processing, which involve cold-reduction and cold-forming. At least one factor contributing to the stiffness of this steel is the relatively high phosphorus content of the acid product. The phosphorus content of the Thomas or basic Bessemer steel of Europe is considerably lower than the normal acid product in America. The American industry has continued the use of the acid process chiefly for the reason that the available ores are more easily adapted to this process from both metallurgical and economic standpoints. In European practice the basic process is necessary with the highly phosphoric ores available and it is sustained to some degree by the sale of the rich phosphate slag as a by-product. The basic process was used in this country at several plants many years ago, but was abandoned for economic reasons. A part of the past history of these trials is given here because the author believes it has not been published and it has some bearing on the subject of this paper. The information is authentic to the extent that

Jan 1, 1941

By S. R. B. Cooke, H. S. Choi, I. Iwasaki

Oleic acid is the chief ingredient of fatty acids used as collectors in nonsulfide flotation. With a few notable exceptions, the various quantities of saturated and other unsaturated acids comprising the remainder are usually unspecified. There have been occasional investigations to determine the collecting ability of these other acids and their effect on collection with oleic acid, but much remains to be done in this field. Hukki and Vartiainen, on the basis of tests using palmitic, oleic, and linoleic acids and an impure linolenic acid, concluded: "The collecting power of fatty acids used in flotation increases with increasing unsaturation of the hydrocarbon chain." ' Their work was concerned mainly with the response of ilmenite to the foregoing collectors, although tests were also made with magnetite, pyrite, hematite, and rutile. Cooke and Nummela, employing an almost identical technical procedure to evaluate flotation of hematite, magnetite, and goethite with various fatty acids, including oleic, linoleic, and linolenic acids of the highest purity obtainable, found: "The effectiveness of 18-carbon unsaturated fatty acids, as collectors for hematite, decreases with increase in the number of non-conjugated double bonds." 2 Vn the foregoing investigations, collector efficacy was measured on the basis of reagent addition in moles per liter. Sources of fatty acids which may be used as collectors are legion, but provided the oleic acid content is high enough, cost is normally the determining factor. Usually this restricts severely the purity of the collector in terms of its oleic acid content. Within the past year or so users of crude oleic acid have become somewhat more discriminating, apparently realizing that some of the organic acid impurities may exert deleterious effects upon certain separations. Marine fish oils have been used as collecting agents, particularly in the earlier days of froth flotation. Currently their use is restricted in this field to relatively minor applications, although they are cheap sources of fatty acids. In an effort to increase the range of uses for fish oils, the U. S. Fish and Wildlife Service has awarded contracts to study these materials as sources of new products suitable for commercial development. Funds for these investigations were provided by the Saltonstall-Ken-nedy Act of 1954. One such contract was awarded to the University of Minnesota School of Mines and Metallurgy for the purpose of investigating the use of fish oil fatty acids and their derivatives in ore flotation. Besides the esters of various saturated aliphatic acids and of palmitoleic and oleic acids, fish oil also contains esters of monoethenoid and polyethenoid acids with 20, 22, and 2 carbon atoms. The basic purpose of the investigation was to determine whether the longer-chained unsaturated acids possess collective properties superior to those of the C,, monoethenoid oleic acid, the C16 monoethenoid palmitoleic acid, or the saturated C,, stearic acid and its shorter chain homologues; whether highly unsaturated acids have merit as collectors; whether rela-

Jan 1, 1960

By R. L. Fullman

Relationships are derived between average dimensions measured on a polished cross section and the spatial dimensions of particles dispersed as uniform cylinders. The equations are applicable to the measurement of rods or plates without the stipulation that they be extremely thin. QUANTITATIVE analysis of the elements of mi-crostructures has been limited by a lack of knowledge concerning the relationships between observations on plane surfaces and the spatial nature of the structure. This paper is an extension of previous efforts to establish equations suitable for the quantitative investigation of microstructures. The equations derived fill two gaps in the range of particle shapes for which measurements may be required, namely those shapes lying between extremely thin plates and equiaxed particles (approximately spherical), and those intermediate between equiaxed particles and extremely thin rods or needles. In a previous paper' equations were developed relating dimensions measured on a polished cross section to the average spatial dimensions of particles in the form of spheres, extremely thin plates, and extremely thin rods. For extremely thin rods the dimensions measured on a polished cross section were found to depend on the radius only, so that no information concerning the rod lengths or number of rods per unit volume could be obtained from observations on a cross section. In this paper equations are derived relating dimensions measured on a polished cross section to the spatial dimensions of particles in the form of identical cylinders. These equations may be used to evaluate the dimensions of rods, as well as the dimensions of plates, without the stipulation that the plates or rods be extremely thin. The impossibility of evaluating the length of extremely thin rods from planar measurements appears as an increase in the amount of data required for a given precision, as the length-radius ratio increases. Consider a sample containing particles of a phase in the form of cylinders of uniform radius T and height t. If the cylinders are randomly oriented, as in a sufficiently large sample of a fine grained poly-crystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the cylinders are not randomly oriented, it is necessary to randomize the orientations of the cross-sectional planes and traverse lines. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of particles N, cut by the cross-sectional plane per unit area is equal to the number of particles N, per unit volume times the probability p1 of a plane intersecting a single randomly positioned and randomly oriented cylinder in the cube. Let J be the maximum cylinder dimension in the direction normal to the cross-section planes, as shown in Fig. 1. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length J

Jan 1, 1954

By J. G. Mravec

The SO-called gas-tube method as developed by Hare, Peterson and Soler for determining the type and content of gases in molten steel is particularly adapted for determining the hydrogen content in molten steel. The development of this method has been quite completely discussed in a paper published by these co-workers in 1937.' The purpose of this paper, therefore, is to familiarize with this method those who arc not well acquainted with it. The principle of the gas-tube method is as fol1ows: One end of an evacuated gas tube is sealed with a very thin copper disk. when this end of the tube is immersed in a test spoonful of molten steel, the copper disk melts almost immediately, allowing a portion of the steel to be drawn up into the evacuated space. Any dissolved gases, and those produced by reactions between the components of the steel during freezing, are liberated into the unfilled portion of the sampling tube. A blob of steel that forms on the immersed end of the tube after the sample is drawn up seals up the end, making it airtight again. The evolved gases are subsequently drawn out of the gas tube through a suitable valve and analyzed by means of an Orsat apparatus. The volume of the sampling tube is sufficiently large so that a pressure considerably below atmospheric is produced after the gas evolution. The low pressure is necessary to effect a nearly complete removal of gases from the steel. Construction oF Sampling Tube The sampling gas-tube apparatus is illustrated in Fig. I. Seamless S.A.E. tubing used for section A is first cut into 7-ft. lengths. Through cxperiencc it was found necessary to use two sizes of tubing for this part, "is-in. and 3/4-in., respectively. The smaller tubing is generally used on the hotter or lower carbon steels. If the inside wall of the tube A is coated with grease or oil, it should be burned out before being machined as follows: One end is machined on the inside diameter to a depth of 34 in., so as to form a seat for a 7/8-in copper disk, which is stamped out from 0.005 to 0.007-in. thick copper sheet. The other end is machined on the outside diameter to a diameter of 1 5/16 in., to take a small reservoir or trap member I?. About 4 in. below the same end, a 1/2-in. hole is drilled to receive the 1/2-in. copper tubing leading to the large reservoir C. The inside of tube A is then thoroughly cleaned with a round wire brush, such as is generally used to clean out shotgun barrels. It is very important that the surface be absolutely free of rust or any nonmetallic coating. Next, the thin copper disk is soldered in place with low-melting silver solder.

Jan 1, 1945

By W. M. McCardell, W. O. Winsauer, M. Williams

The mechanism by which an electrical potential difference is developed between two salt solutions separated by shale is shown to be a consequence of the electrical double layer of the shale surfaces. A mathematical derivation is presented to show -the dependence of the potential on the shale characteristic.? and on the concentration of the salt solutions. The equations developed describe adequately the potential-concentration behavior of a long shale core. The equations also describe the variation of potential of sand-shale mixtures with variation of clay content. Ion adsorption i* an important factor in he developments of the surface charge on the shale. and electrical resistivity and ion transference number data are emlployed to estimate the increase of surface charge with concentration. Since the potential is shown to be dependent on the characteristics of the particular .system. water salinities estimated from the potential log by previously proposed methods may be low in some rase;. INTRODUCTION That the electric well log exists today may he attributed to the ingenuity of the Schlumberger brothers who adapted to the logging of wells techniques which were originally developed as surface prospecting methods for the location of ore bodies Empirically it was found that the potential curve of the electric log usually gave values for clean sands which were negative with respect to the values for shales. It was suggested that the potential was responsive to porosity. It was postulated in explanation? that the potential was the sum of a streaming potential, which differed for sands and shales, and of an "electro-chemical" potential of undetermined origin. Mounce and Rust in 1943 showed that the streaming potential is small in most cases and that the potential is generated by a process in which shale and a salinity difference play-essential party. Dickey.:' in the same year, concluded that the potential is dependent upon adsorptive properties of reservoir rock. Wyllie in 1949. and Wyllie and Patnode, in 1950, measured the potential-: between two salt solutions separated by barriers of either naturally-compacted or artificially-compacted shales and concluded that the potential can be expressed by where E is the potential R is the gas content F is Faraday's constant T is the absolute temperature are the activities of the two uni-univalent solutions These authors postulated that shale. in the ideal case is impermeable to the migration of negative ions. Any potential less than the "ideal" shale potential was considered to be due to imperfections in the shale barrier. Although the studies by Wyllie and Patnode of the development of the shale potential are fairly recent. investigators in fields other than well logging have discussed the mechanisms responsible for analogous potentials over a period of several decades. Although it is evident that much thought has been devoted to the question of the origin of the potential observed in wells, it is also apparent that all of the explanations presented to

Jan 1, 1953

By J. S. Marsh

Joseph Priestley prepared oxygen on Aug. I, 1774, and noted with great surprise "that a candle burned in this air with a remarkable brilliant flame." On Aug. 2, 1774, some ironmaker possibly began to wonder if this substance could be used to increase his rate of production; at any rate, there is no disputing the fact that the notion of using oxygen for steelmaking in concentrations greater than that available in great abundance—as air—has been in existence for years. Action was delayed by the lack of enough oxygen at a cost within reach of the steelmaker. Within the last several years enough has been available to permit large-scale tests of its use for both combustion, with which this paper is concerned, and for decarburization. The literature is now enormous and easily available; it is sufficient here to cite three items of historic importance in that all are about 25 years old and in that all are remarkably consistent as far as they go, with what is known today.1,2,3 Significance of High-temperature Heat The principal function of the open-hearth furnace is to supply sufficient high-temperature heat to melt the charge and then to increase its temperature to a range suitable for tapping, ordinarily in the neighborhood of 2900°F. That heat is required to make steel is understood by everybody; however, there seems to be some confusion now and then about the significance of high-temperature heat. Transfer of energy—and heat is energy— is always from a point of higher potential to a point of lower potential and, other things being equal, the greater the potential difference, the greater is the rate of transfer of energy. In the open hearth the flame, of course, is the high-potential source. Perhaps the most satisfactory approach is through the notion of theoretical flame temperature, which is the ratio of heat input to the heat content of the combustion products,* the former is composed mainly of heat of combustion of the fuel plus sensible heat of the fuel plus sensible heat of the combustion air. Thus, flame temperature can be increased by increasing the value of the numerator, by decreasing the value of the denominator, or both. The first method is as old as the open-hearth process and, of course, makes use of preheated air; its possibilities have been by no means exhausted. The second method can be put into effect only by changing the composition of the combustion air, since the combustion of a given quantity of fuel produces a definite quantity of product, and since the denominator includes the non-reactive fraction of the air, principally nitrogen. In other words, the denominator consists of the volume of exit gas multiplied by its heat capacity and that volume consists of carbon dioxide and water vapor as reaction

Jan 1, 1949

By P. K. Foster, A. McNabb

A consideration of the literature shows the inadequacy of Fick's Laws to describe the diffusion of hydrogen in steels below 400°C. These laws are modified an the assumption that hydrogen is delayed at fixed sites in the lattice. Approximate and exact solutions of the resulting nonlinear system are derived for simple geometrical shapes. The results qualitatively account for the observed anomalous behavior. Experimental methods for verifying the theory are suggested. 1 HIS paper presents a new analysis of the diffusion behavior of hydrogen in steel based on a physical model which supposes that hydrogen atoms wander in a random manner through the crystal lattice, but tend to get trapped or delayed at certain fixed sites uniformly distributed throughout the metal. These sites, which will be called traps, are regarded merely as potential wells of significantly greater depth than those encountered in regular regions of the crystal lattices and no assumptions are made concerning their nature or origin. The results of experimental studies of the diffusion of hydrogen in iron and steel have usually been reported in the literature in terms of a diffusion constant D derived under the assumptions that the hydrogen concentration C is governed by Fick's laws.1 Fig. I is a composite of published graphs of the man. ner in which the values of D, so derived, vary with temperature. It is convenient to consider this material in two categories; the high temperature results above 400°C, and the results at lower temperatures. The graphs 2, 3, 4, 5 in the first class lie within a factor of three of each other and are relatively consistent compared with the low-temperature values. There is an increasing divergence in values of D with decreasing temperature till at room temperature they are spread over three orders of magnitude. Small values of D have been obtained for work-hardened specimens.' It is evident that D is a function of other variables besides temperature in this range and that these neglected variables are in some way connected with the work hardening experienced by the specimen. In view of evidence for an interaction between hydrogen in solution and dislocations9'10 and adsorption on crack surfaces,' some doubts must be entertained about the validity of Fick's laws and their associated physical model of noninteracting particles in random motion through the medium. More direct evidence of their inapplicability to the diffusion of hydrogen in steel was first produced by Darken and smith." Consider the permeation of hydrogen through a plate of thickness a under a boundary concentration Co at the ingoing, and zero at the outgoing, face. If Fick's first law1 is valid, the steady state flux P, through unit area is DCo/a. In addition, the concentration C varies linearly throughout and Qo, the mean quantity of hydrogen in the medium, is co/2. Compare Qo with Q1 the mean quantity required to saturate the same specimen to a uniform concentration G. In this case Ql = Co and hence the ratio

Jan 1, 1963

By L. Burris, G. A. Bennett, P. A. Nelson

Staznless steels ave rrzuch less seuel-ely attacketl by zinc lapov than by molten zinc systems. To determine the applicubility of stainless steels fov equipment items which would be exposed only to zinc vapor, the corvosion resistance of several stainless steels to zinc vapor was investigated in 500-hr- exposuves at 900° C. Two austenilic stainless steels, Types 304 and 3-17, suffered severe intergranular attack. Loss of nickel from these steels and micro-probe crnalyses indicated the probable formation of low-melting zinc-rich phases. Good vesistance to attack by zinc vapor, as determined by metallo-9-rpaphic excr)rtination and physical testing, Loas exhibited by Type 405 stainless steel, a jevvitic steel. Type 440C stainless steel, a tnartensitic steel, although suffering considevable loss in weight, was not structurally weakened. At Argonne National Laboratory liquid zinc and zinc-rich alloys are being employed as solvent media in pyrometallurgical processes under development for recovering and purifying discharged reactor-fuel materials.' Because of the high solubility of most metals in liquid zinc,' there are few metals which can serve as container materials for liquid zinc at temperatures much above the melting point. The poor corrosion resistance of the common metals and alloys to molten zinc has been discussed by Eldred.3 DeKany, Lavendel, and Burris4 tested some of the less-common alloys of the nonrefractory metals and found that they also have poor resistance to attack by liquid zinc and Zn-Mg solutions. Of the metallic materials, only some of the refractory metals such as tantalum, tungsten, and molybdenum and their alloys have shown resistance to attack by liquid zinc.4-7 In the process-development work at Argonne National Laboratory, tantalum and tungsten vessels have been used to hold liquid-zinc alloys. These vessels are housed in stainless-steel equipment, principally to permit maintenance of an inert atmosphere and operation at various pressures. In this experimental work, it has often been observed that Type 304 stainless steel suffers little attack by zinc vapor at temperatures up to about 800 °C. In contrast, severe attack occurs in areas where zinc condenses as a liquid. The extent of attack by zinc vapor on several stainless steels was investigated because there are possible useful applications of stainless steel for equipment items which would be exposed only to attack by zinc vapor. These applications include, for example, housings around processing equipment as indicated above and vapor lines leading from zinc stillpots or retorts to condensers. EXPERIMENTAL EQUIPMENT AND PROCEDURE The experimental procedure consisted in exposing stainless-steel test coupons to static zinc vapor for 500 hr at a temperature of about 900°C. The apparatus, shown in Fig. 1, consisted of a 12-in.-long closed tantalum tube jacketed in Type 304 stainless steel to prevent oxidation of the tantalum. A Zn-10 wtpct Mg* alloy charge of 293 g in the bottom of the

Jan 1, 1965

By E. H. Lancaster, M. E. Mitchell

A MUD-conditioning program found to be very effective for drilling and completion operations on routine field wells requiring relatively short drilling time involves a moderate alkaline-tannate-bentonite treatment resulting in an ultimate filtration rate of 10.0 cc or less (API test). Mud weight schedules are planned from pressure information on completed wells in producing reservoirs and drill-stem test data obtained on other zones not being produced at present. In general, terminal mud viscosities average 45 sec (Marsh). This value has been found to be sufficient to remove cuttings from the well bore on the average well, with the slush pumps in general use on the rigs. On field wells requiring drilling times in excess of approximately 30 days, an alkaline-tannate-lime-bentonite treatment has been effective in maintaining desirable viscosities and filtration rates with a substantial reduction in chemical costs. This system has shown particular advantage on heavily weighted muds and those with abnormal flow-line temperatures. For the most part, the chemical treatment utilized in wildcat drilling follows closely the program used on field wells, depending on depth and duration of drilling operations. Wildcat mud programs are planned from information available from various geologic and operational sources, taking into consideration the possibility of encountering mud problems of a special nature in the wildcat area. Careful planning of wildcat mud pro- grams has proved to have definite value in avoiding most serious mud problems. An analysis and recommended treatment are presented on several special. mud problems which have been encountered in the area in the past. Those problems discussed are lost circulation, blowouts, sloughing shale, excessive chloride contamination, sulphate contamination, and prevention and correction of cement contamination. Introduction Drilling-mud control in the Southwest Texas area, in general, does not involve the multiplicity of problems encountered in other coastal areas. For instance, it is rare that a mixture of problems such as lost circulation, abnormal pressure, severe sloughing shale, and others, occurs on one well within close enough limits in vertical depth not to be taken care of by a sensible casing program, together with a relatively clear-cut mud program. There are conditions such as the fairly widespread occurrence of abnormal pressure in the lower Frio and Vicksburg zones, and the tendency for sloughing shale in the Jackson section which make for rather expensive mud control. However, the availability of fairly accurate geologic and operational information makes possible a reasonable degree of standardization on mud treatment over a relatively large area. It may be said that, over most of this area where drilling is currently in progress, the natural mud made is very poor in quality, but responds readily to moderate chemical treatment to yield very good wall-building characteristics. AS far as field development drilling is concerned, the mud engineer's principal job, once the routine treatment best

Jan 1, 1949

By A. W. Gauger

It is with some trepidation that I approach my subject, for I know that I shall at once incur the suspicion of the mechanical engineer, with his concern for boiler tests and efficiencies; of the mining engineer, with his mechanization problems; and of the chemical engineer with his unit processes. Nevertheless, it must be recognized that the technology of fuels, the systematic body of knowledge relating to the production, processing and utilization of mineral fuels, has grown to such proportions and involves so many widely diverse applications of fundamental science and engineering that it behooves us to stop and consider just what its status is in relation to other technologies, as well as in relation to the present and future needs of the social order. The time has come when technologists, applied scientists and engineers must consider the possible effects that their achievements may have on Society. The development of a machine to - -replace -several hundred men is a fine achievement when considered solely from the point of view of creative endeavor. But what of the men who are displaced by the machine! Does not the responsibility for the development of this machine embrace as well the consequences of obsolescence and technological unemployment resulting from such development? I believe that it does and that we must recognize this fact in our practice of engineering and tech- nology as well as in the training of future engineers and technologists. Magnitude of the Fuels Industry Fuel technology is the body of knowledge that relates to the mineral fuels. The fuels industry is by far the most important of all Our mineral industries. The chart in Fig. I, reprinted from U. S. Bureau of Mines Information Circular No. 6643, indicates the compartive values of metals, fuels and other nonmetallic minerals for the year 1929. Of the grand total of 13¼ billions of dollars in value of minerals at the mines, the mineral fuels contributed 48 per cent. Coal, with 34.4 Per cent, exceeded the value of any other single mineral. In fact, the value of the production of the Pennsylvania anthracite mines alone anand exceeds the value of the gold production of the entire world. Petroleum and natural gas in 1929 contributed 14.3 per cent and 3.3 per cent, respectively, of the total value of world mineral production. So much for the world picture; let us now look at the situation in the United States. Over the 60-year period 1880 to '939, $46,409,727,000 of metal1ic products, $80,788,852,000 of fuels (coal, petroleum, natural gas, natural gasoline) and $27,871,-ooo,ooo of nonmetallic minerals other than fuels were produced. The mineral fuels have contributed 52.7 per cent of the entire mineral wealth produced over this period that has seen such tremendous industrial development in our Our As a matter of fact, our present industrial civilization has been made possible through the use of the

Jan 1, 1942

By H. I. Najarian

This paper is a companion piece to the description of the electrothermic process that begins on page 141. It will be confined to a brief story of the development. of the Weaton-Najarian vacuum condenserf at this plant, together with up-to-date design and operating data. The Josephtown smelter was designed primarily for production of zinc oxide. However, the development of a method for production of zinc metal had always been under consideration, and accordingly one of the original eight units of the elcctro-thermic furnaces built in 1930 was set up to produce metal. The design of this furnace was identical with that of the oxide furnaces except that in place of oxide tewels opening into oxide manifolds, conventional conical clay condensers—similar to condensers used in horizontal retort smelting—were installed around the periphery of the furnace and in several tiers vertically for condensing the zinc vapors. The early experimental work in trying to condense zinc out of the mixtures of zinc vapor and carbon monoxide gas from the electrothermic furnaces indicated that, while the gases from electrothermic smelting would condense in surface-type condensers, the formation of blue powder was excessive and condenser efficiency low. Furthermore, operating a large unit of electric furnace with several hundred small condensers, with attendant high labor cost and unfavorable operating conditions, did not appeal to us. We also realized that a single unit of surface condenser capable of condensing 12 torg tons of metal per day would be of huge dimensions and possibly difficult of control. So we took as our aim the development of a method whereby a single condenser unit of reasonable dimensions would condense zinc, in one step, from the large volume of gases that the electric furnaces produced. We set about searching for knowledge on zinc metallurgy and design of zinc condensers in particular. Our study of the prior art focused our attention on the oft-repeated statement by earlier experimenters, that the most efficient way to condense metallic vapors, such as zinc vapors, was to bring the vapors into "intimate contact" with molten metal; but the methods offered for securing this "intimate contact" in any practical manner left much to the imagination. We were handicapped by not having some-one on the Josephtown smelter staff who could lay claim to being an expert zinc metallurgist and could give guidance from actual experience on the practicability of various schemes that haunted our imagination. Laboratory Experiments However, we had an expert ex-steam engineer in the person of George I?. Weaton, manager of the Josephtown smelter, who had had long experience with steam-jet condensers and would reiterate his belief at every opportunity that the logical and the most efficient way to condense zinc would be with a jet-type condenser. We became intrigued by the possibilities of a zinc con-

Jan 1, 1944

By Michael Perch, Charles C. Russell

The fact that coal is a complex organic material and heterogeneous in composition has made its study extremely difficult, particularly in regard to obtaining a fundamental concept of the processes involved in the formation of coke. It has been stated1 recently that coals are natural polymers and that in a complex reaction such as occurs during carbonization the differences between coals are quantitative and not qualitative. Such being the case, it would be expected, therefore, that a series of coals subjected to exactly the same conditions of coking would produce results that should be related quantitatively to the chemical analyses of the individual coals. In the past, however, this fact was not generally recognized and consequently many empirical test methods were devised for testing coals. The interpretation of the results obtained depended upon comparing a set of data with other data on coals of known characteristics. The testing procedure had to be conducted in precisely the same manner each time and not the least requirement in making the interpretation was experience. The test methods varied from those utilizing a gram of coal to the plant-scale tests in which one or more ovens were charged with the test coal. The aim had been principally to find some simple, inexpensive means by which the coke-making and other properties of coal could be predicted. It is not necessary to emphasize the importance of these endeavors, for anyone acquainted with the problems involved in the selection of coals for making coke is well aware of the time and expense involved in making a series of definitive tests. Several attempts have been made to derive formulas for such predictions. The relations of both ultimate and proximate analyses to coke physical properties and byproduct yields have been studied. Lowry and co-workers1 correlated statistically the U. S. Bureau of Mines-American Gas Association assay test results with coal analyses, using 90 coals and coal blends. Parry,² Spooner,3 and Gabinskii and Krym4 made similar correlations. Lowry concluded that there were definite relationships between the proximate analyses of the coals and the yields and properties of the products. Although this statistical study was made on test results from carbonizing coal in a cylindrical steel retort, the conclusions are important and provided one of the first steps in the simplification of this complex subject. Studies should be made of other references on this subject just cited. Studies of the coking process reported in the literature frequently were confined to a small number of coals, and very few have included coals from various ranks. It would seem logical, however, that a program for studying factors involved in the formation of coke should be based on a number of coals selected from each of the various classes or types of coking coal. The possible use of the scheme of classifi-

Jan 1, 1950

By Toshimi Yamane

The internal friction of cold-worked titanium iso-thermally annealed at temperature below the recrystallization temperature was measured. The internal friction was calculated from the half width of a resonance curve of the specimen which was vibrated transversally by the electromagnetic method. The experimental results were as follows: 1) The specimens annealed for a long time at temperature below the re crystallization temperature after cold working have the strain-amplitude dependent internal friction. 2) The internal friction increased by the cold working was decreased during the isothermal annealing. The reason of decrease of the internal friction is considered to be caused by the annihi-lation of lattice defects. 3) There is a linear relation between logQt-1/Q0-1 and (1/T)2/3 below the recrys-tallization temperature, where Q0-1 is the internal friction standing 24 hr at the room temperature after cold rolling, Qt-1 is the internal friction annealed at T°K for t min. 4) The hardness of the cold-worked titanium does not change by the annealing at 300°C for a long time but decreases by annealing at 400ºand 460°C. METALS, when cold worked, show sharp changes in physical and mechanical properties' The internal friction of cold-worked metals increases sharply and has a maximum value1,2 connected with working de- grees. The increased internal friction of cold-worked metals is recovered by annealing. This phenomenon is the well known effect called Köster effect. The recovery of the internal friction occurs earlier than the changes in tensile properties, hardness, or X-ray diffraction, and is very sensitive to the structure of a metal. The mechanism of the recovery at a temperature lower than the recrystallization temperature is being considered variously by many investigators: there are such views as the annihilation of dislocations by smith,' the rearrangement of dislocations mentioned by Nowick,4 and interaction of dislocation with point defects.5 Smith and Nowick also considered the interaction but it is so difficult for them to explain the rearrangement mechanism systematically, it being not considered a special model; therefore, we do not explain it quantitatively. Experiments measuring the recovery of the internal friction of cold-worked metals were performed by Gordon and Nowick6 on NaCl, and by Smith on copper. In addition, there are many studies, particularly those of measurements on copper by other investigators. There are comparatively many investigations on aluminum and iron which are the cubic system,'-' but only a few on metals of the hexagonal system.10 In view of this, I investigated cph titanium at room temperature and measured the internal friction after annealing isothermally at temperature lower than the recrystallization temperature. SAMPLES AND EXPERIMENTAL METHOD samples for the experiment were cut from a 6-mm titanium plate. The long direction of samples was

Jan 1, 1963

By H. C. Howard

Reaction of oxygen and bituminous coal starts as soon as the coal bed is exposed to air and, with some coals, proceeds with significant velocity even at normal temperatures and at normal oxygen partial pressures of one-fifth of an atmosphere. At higher temperatures, the reaction is greatly accelerated and ultimately a condition is reached where the process is very rapid and we then speak of combustion. It is the purpose of the present paper to discuss the reactions of oxygen and coal at temperatures below those of active combustion. It is these low temperature oxidation reactions which are responsible for heating in storage and for marked changes in agglutinating proper-ties. These reactions may also be employed for the preparation of organic acids, which are of direct interest to the chemical industry. For convenience in discussion, the low temperature reactions of oxygen and bituminous coal can be roughly divided into three stages though there is, of course, overlapping. Stage I is a surface oxidation stage, characterized by the addition of oxygen, with the formation of oxygen containing groups some of which have acidic properties. Carbon dioxide, carbon monoxide and water may be formed con-comitantly and are always liberated at higher temperatures, and in cases where the oxidation is prolonged. Superficially, the coal is little affected by this primary stage of oxidation and usually only minor changes in ultimate composition result. There may be definite changes in coking and coking properties, and heat of combustion susceptibility to further oxidation. The presence of acidic groups can be demonstrated by specific reactions. These groups may show cation exchange properties like the mineral zeolites. The formation of oxalic acid has been reported. If the oxidation is continued, a large fraction of the organic material of the coal is converted ultimately into alkali soluble, acid insoluble products, which have been given the name "regenerated humic acids" and which are the characteristic products of Stage 2. These humic acids, in the solid stage, do not differ greatly in appearance from the original coal, but show large differences in chemical composition and chemical and physical properties. Along with the humic acids, carbon dioxide and some of the water soluble types of Stage 3, are also formed. If the oxidation is carried still further, the humic acids may be degraded completely to the simpler, lower molecular weight acids of Stage 3 which are characterized by solubility in acid as well as in alkaline media, and by their orange, yellow or white colors. Additional carbon dioxide is formed in the transformation from Stage 2 to Stage 3 and, for a number of American coals, a maximum yield of the water soluble types of acids is reached when about 50 pct of the carbon of the coal is converted to carbon dioxide. Primary Oxidation The initial step in the reaction of gaseous oxygen on coal, like that on carbon,

Jan 1, 1949

By David W. Mitchell

WHILE pure magnesium does not corrode rapidly the presence of even very small quantities of certain other metals accelerates corrosion remarkably. Because magnesium is such an electropositive metal (E° = +2.34 volts)' the presence of substances that permit galvanic activity is extremely undesirable. It is stated that as little as 0.017 pct of iron in magnesium causes a marked increase in the corrosion rate.2 Magnesium and its alloys are commonly melted in iron or steel pots; consequently the commercial metal has the opportunity to pick up iron if it has that tendency. Quantitative data on the solubility of iron in magnesium are of practical as well as of academic interest. Some magnesium alloy castings tend to have large grain size unless suitable treatment is given to the liquid metal just prior to casting. One method of grain refinement consists of "superheating" the metal just prior to casting. "Superheating" is heating to a temperature 100 to 200°C above the casting temperature and holding for a short period of time. Superheated metal has a much finer grain than unsuperheated metal. A satisfactory explanation of this phenomenon has not been forthcoming. One hypothesis attributes the grain refinement in the superheated metal to precipitation of some phase that is miscible at the temperature of superheat but not miscible just below the casting temperature and which is thought to provide nucleating centers for crystallization. This phase, if the foregoing hypothesis is correct, would probably be a metal or an intermetallic compound. Of the metals likely to be found in magnesium alloys, iron is one of the most likely candidates for the role of grain refiner for iron occurs in small quantities in all commercial magnesium and magnesium alloys. A. Beck' states that magnesium, in either the liquid or the solid state, cannot dissolve iron and that iron exists as a finely divided suspension which does not settle out because of its extreme fineness. Beck also presents a micrograph showing a large iron dendrite in magnesium but does not comment on the crystallization of iron from a solution supposed to contain none. It is doubtful that dendrite formation from suspended iron would be possible. This suspension theory is the basis of patents4 covering the removal of iron from magnesium by allowing the iron particles to act as nuclei for the formation of primary magnesium crystals which can be separated by segregation. Also covered by patents is the removal of iron by the addition of another metal to form an intermetallic compound with the iron which, because of its increased particle size, is able to settle out of the molten metal. Here, too, quantitative information on the extent of iron solubility in liquid magnesium is of more than theoretical interest. M. Hansen,5 in his critical collection of the data on binary alloys, states that iron is not soluble in liquid magnesium. W. R. D. Jones6 who studied the physical properties of low iron magnesium alloys observed a

Jan 1, 1948

By R. G. Jones, W. L. Kinney, R. E. Schilson, R. S. Wilson, G. A. Clark, H. Suralo

This paper describes the field opeturluns at the Fry in situ combustion project in Crawford County, 111. Field operations may be divided into three phases—-preliminary engineering studies of 1960 and 1961, ignition, and, finally, operation of the test. The Fry combustion project was a pilot test of cocur-rent in situ combustion on a 3.3-acre inverted five-spot. In the summer of 1960, air injection tests were conducted using old wells in the area and a new air injection well drilled especially for the test. In the summer of 1961, four new oil wells were drilled on a 3.3-acre pattern for the pilot test. All old wells in the near vicinity of the pilot test were abandoned to preclude any possibility of gas escaping to adjacent formations. A compressor plant was also installed at the test site in 1961. Air injection tests and other engineering studies were made. At the conclusion of these tests, ignition was accomplished with a 40 kw electrical igniter. Operation of the Fry combustion test was little different from the usual oilfield operation with the exception of the high rate of air injection. No difficulty was found with the openhole completion. There were no unusual corrosion or emulsion problems until bottom-hole temperatures exceeded 150F. Four cores were drilled into the burned-out portion of the reservoir with no mechanical difficulties. INTRODUCTION A cocurrent or conventional in situ combustion test was conducted on the Fry unit of the Marathon Oil Co., in Crawford County, Ill. Besides testing combustion in the Fry type of reservoir, the test was intended to evaluate various operating procedures. This paper presents a discussion of the Fry combustion test field operations. The geology of the reservoir and the test performance are discussed in other papers.'.' HISTORY OF THE FRY UNIT The Fry unit consists of 11 leases totaling 337 acres in an area in which oil was originally discovered in 1906. Production from this reservoir, as from all Robinson sand reservoirs in the area, was very high during the first few years. As the dissolved-gas energy was dissipated, early attempts to retard the decline consisted of vacuum, air, and gas repressuring, and recently, most of the area has been subjected to water flooding. Following early air repressuring, the Fry waterflood unit was formed and water flooding initiated in July, 1952. In the area in which the Fry combustion test was conducted, a peripheral water flood of a 160-acre area was developed as shown in Fig. 1. Between 1956 and 1960, it became apparent that the water flood was unsuccessfd. In looking for a suitable site for an in situ combustion test, the Marathon Oil Co. selected the Fry unit as possessing those features most desirable for such a research project. Field operations associated with the Fry combustion test began in the spring of 1960.

Jan 1, 1966

By A. W. Gauger

It is with some trepidation that I approach my subject, for I know that I shall at once incur the suspicion of the mechanical engineer, with his concern for boiler tests and efficiencies; of the mining engineer, with his mechanization problems; and of the chemical engineer with his unit processes. Nevertheless, it must be recognized that the technology of fuels, the systematic body of knowledge relating to the production, processing and utilization of mineral fuels, has grown to such proportions and involves so many widely diverse applications of fundamental science and engineering that it behooves us to stop and consider just what its status is in relation to other technologies, as well as in relation to the present and future needs of the social order. The time has come when technologists, applied scientists and engineers must consider the possible effects that their achievements may have on Society. The development of a machine to - -replace -several hundred men is a fine achievement when considered solely from the point of view of creative endeavor. But what of the men who are displaced by the machine! Does not the responsibility for the development of this machine embrace as well the consequences of obsolescence and technological unemployment resulting from such development? I believe that it does and that we must recognize this fact in our practice of engineering and tech- nology as well as in the training of future engineers and technologists. Magnitude of the Fuels Industry Fuel technology is the body of knowledge that relates to the mineral fuels. The fuels industry is by far the most important of all Our mineral industries. The chart in Fig. I, reprinted from U. S. Bureau of Mines Information Circular No. 6643, indicates the compartive values of metals, fuels and other nonmetallic minerals for the year 1929. Of the grand total of 13¼ billions of dollars in value of minerals at the mines, the mineral fuels contributed 48 per cent. Coal, with 34.4 Per cent, exceeded the value of any other single mineral. In fact, the value of the production of the Pennsylvania anthracite mines alone anand exceeds the value of the gold production of the entire world. Petroleum and natural gas in 1929 contributed 14.3 per cent and 3.3 per cent, respectively, of the total value of world mineral production. So much for the world picture; let us now look at the situation in the United States. Over the 60-year period 1880 to '939, $46,409,727,000 of metal1ic products, $80,788,852,000 of fuels (coal, petroleum, natural gas, natural gasoline) and $27,871,-ooo,ooo of nonmetallic minerals other than fuels were produced. The mineral fuels have contributed 52.7 per cent of the entire mineral wealth produced over this period that has seen such tremendous industrial development in our Our As a matter of fact, our present industrial civilization has been made possible through the use of the

Jan 1, 1942