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By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young's modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu' have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young's modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu' pointed out, calculated variations in Young's modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young's modulus, the shear modulus and Poisson's ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young's modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

Secretary Membership Committee Increase of Membership Papers and Publications Committee Library Committee Treasurer Report of the Secretary TO THE BOARDOF DIRECTORASN D THE MEMBEROS F THE AMERICANIN STITUTE OF MINING AND METALLURGICAENL GINEERS GENTLEME:N As will be shown by the special reports of the Finance, Membership, Library, Papers and Publications, Increase of Membership, and other standing Committees, together with that of the Treasurer, the year 1927 was one in which the Institute made very satisfactory progress in a number of directions. In total numbers the membership is no larger but in revenue from dues there has been a marked increase. This has been due to the promotion to full membership of Junior Associates of earlier years, to the larger proportion that come in originally as members rather than juniors, and to the keener interest in the work of the Institute reflected in prompter payment of dues. The latter is important, since experience shows that of those who fall behind a large number must ultimately be dropped for non-payment. Conditions in the mining industries have been healthy though not booming. It has been much easier for members to find employment and meet their financial obligations but there has not been that flow of young men into mining, and hence in part into the Institute, that characterized certain earlier years. Rather the tendency toward centralization and larger industrial units has restricted the number, though not the scope, of opportunities for technical men in the mineral industries. The Institute is constantly receiving resignations from members crowded out of mining into other lines of activity. On the other hand, those who remain in mining and metallurgy have a greatly increased necessity for i,dormation and contacts with technology. A few years ago many superintendents and most foremen were non-technical men. Today the reverse rule obtains and shift bosses and men who occupy even lower positions in industrial units are called upon to know and to apply such an amount of technical knowledge that graduate engineers are the rule rather than the exception. The curious situation has obtained that with a much smaller enrolment of students in the schools of mining and metallurgy there has been at times an actual shortage of young engineers for beginners' jobs. The young men retort that the conditions of employment and pay offered in mining are not equal to those in other lines and, while it is undoubtedly true that the young engineer beginning in mining is able to start under conditions markedly better as to pay, living, and responsibility than did the men who are now leaders, they are required to know much more and have usually spent more in time and money to qualify for their jobs. The whole matter is one which warrants much more attention than has been given to it. For the Institute it is important since the young men

Jan 1, 1928

By D. B Kibler

The Florida hard-rock field extends from Suwanee and Columbia Counties in northwest Florida to south of Croom, Florida, in Hernando County. This area is approximately 100 miles long and varies from 2 to 30 miles in width. Florida hard-rock phosphate was discovered at Hale Springs, about one mile northwest of the town of Dunnellon, Marion County, in the year 1888, by Alber-tus Voight, who lived within a few hundred yards of the spring. Soon after this discovery there was a great influx of land speculators and wildcat operators into the vicinity of Dunnellon. A few years later phosphate was found in Alachua, Levy, Citrus and Hernando Counties, and a great number of small crude plants were built from Newberry, Alachua County, all the way to Croom, Hernando County. Phosphate was found in many places as "outcrops." Looking for outcrops was the first method used by the early prospectors in searching for deposits. Several years passed before any systematic method of prospecting was used. Early Mining The early method of mining hard-rock phosphate was with picks and shovels, wheelbarrows, mules and wagons. The pick-and-shovel method was used altogether until about 1900, when some of the larger operators began to use railroad-type steam shovels of from ½ to I-yd. capacity Picks and shovels, with negro labor loading the phosphate ore (called "matrix") into wooden side-dump skip-cars, was continued until about 1907. From the discovery of hard-rock phosphate until approximately 1905, overburden was removed with mules and scrapers. At some places, the overburden was loaded into side-dump skip-cars by negro laborers and the cars were then pulled up an incline with a steam hoisting engine. The maximum depth of overburden that could be economically removed by hand labor, mules and scrapers was approximately 15 feet. About 1905 one of the companies erected a producer-gas power- I house near Dunnellon and generated its own electricity and about the same time the larger companies began using hydraulic methods for the removal of overburden. From the year 1888 through the year 1939 approximately 75 companies were operating at one time or another in the hard-rock territory, on approximately 500 locations. The hard-rock deposits are more irregular and have higher mining costs than the pebble-rock deposits, therefore 1 they have not been competitive in the domestic market, but because of the higher grade of the hard rock it is in demand for I the export trade. Discovery of phosphate outside of the United States has made it increasingly difficult in recent years for the hard-rock companies to survive, so today i only three companies are operating. These

Jan 1, 1942

By D. B. Kibler

The Florida hard-rock field extends from Suwanee and Columbia Counties in northwest Florida to south of Croom, Florida, in Hernando County. This area is approximately 100 miles long and varies from 2 to 30 miles in width. Florida hard-rock phosphate was discovered at Hale Springs, about one mile northwest of the town of Dunnellon, Marion County, in the year 1888, by Alber-tus Voight, who lived within a few hundred yards of the spring. Soon after this discovery there was a great influx of land speculators and wildcat operators into the vicinity of Dunnellon. A few years later phosphate was found in Alachua, Levy, Citrus and Hernando Counties, and a great number of small crude plants were built from Newberry, Alachua County, all the way to Croom, Hernando County. Phosphate was found in many places as "outcrops." Looking for outcrops was the first method used by the early prospectors in searching for deposits. Several years passed before any systematic method of prospecting was used. Early Mining The early method of mining hard-rock phosphate was with picks and shovels, wheelbarrows, mules and wagons. The pick-and-shovel method was used altogether until about 1900, when some of the larger operators began to use railroad-type steam shovels of from ½ to I-yd. capacity Picks and shovels, with negro labor loading the phosphate ore (called "matrix") into wooden side-dump skip-cars, was continued until about 1907. From the discovery of hard-rock phosphate until approximately 1905, overburden was removed with mules and scrapers. At some places, the overburden was loaded into side-dump skip-cars by negro laborers and the cars were then pulled up an incline with a steam hoisting engine. The maximum depth of overburden that could be economically removed by hand labor, mules and scrapers was approximately 15 feet. About 1905 one of the companies erected a producer-gas power- I house near Dunnellon and generated its own electricity and about the same time the larger companies began using hydraulic methods for the removal of overburden. From the year 1888 through the year 1939 approximately 75 companies were operating at one time or another in the hard-rock territory, on approximately 500 locations. The hard-rock deposits are more irregular and have higher mining costs than the pebble-rock deposits, therefore 1 they have not been competitive in the domestic market, but because of the higher grade of the hard rock it is in demand for I the export trade. Discovery of phosphate outside of the United States has made it increasingly difficult in recent years for the hard-rock companies to survive, so today i only three companies are operating. These

Jan 1, 1942

By J. E. Burke

Recent investigations have elucidated many of the phenomena of the grain growth process, but have also revealed some conflicting and unexplained results. Beck and his co-workers 1,2,3 have shown that grain growth continues with continued heating at one temperature until the average grain size approaches the thickness of the specimen. Plotting the logarithm of the average grain diameter, D, against the logarithm of the annealing time, t, they find the straight line relationship given by the equation: D = Ktm [,] with possible small deviations at short annealing times. K and n are constants at constant temperature. On the other hand, Wa1ker4 finds that, in alpha brass) the rate of growth falls off more rapidly than indicated by Eq i after long annealing, so that an equilibrium grain size is approached. Burke5 showed, using Walker's data, that time and temperature for grain growth are apparently related through an activation energy, H, according to the relationship: ] where h and tz are the annealing times necessary for the average grain size to increase from Do to D at temperatures T1 and T2 and R is the gas laws constant. In the case quoted, H had the value 60,000 cal per mol. The apparent validity of this relationship, at least up to 700°C, and the approximate value of H were later confirmed by Beck3 The results obtained by Beck Kremer, Demer and Holzworth2 for aluminum and aluminum-magnesium alloys could not be satisfied by such a relationship, since the slope of the isothermal curves increased with increasing temperature. These data indicate and Beck, Holzworth and HuV ater demonstrated expcrimentally that the only apparent factor controlling the rate of grain growth at constant temperature is the grain size. While many of the phenomena have been elucidated, a reasonably quantitative explanation of the process is lacking. There exists uncertainty even as to the primary driving force for grain growth, although there is a considerable body of indirect evidence that the interfacial energy of the grain boundary is responsible.7,8,io Making implicit use of this assumption, several authors14,16 have pointed out that grain boundaries should migrate toward their center of curvature. Harker and Parkerg have advanced this concept furthest, and show that one can expect grain boundary migration to occur only when the grain faces are curved, or when they meet at non-equilibrium angles. When the face is curved toward a grain A, for example, the atoms in the surface of grain B, on the other side of the boundary7 are on the average more surromded by the atoms of their lattice than the atoms on the surface of grain A. Because of thermal motion, the atoms at the interface will sometimes be attached to grain A and

Jan 1, 1949

By Hans Lundberg

FOR the last 20 years, geophysical methods have been in practical use. The results accumulated during this time have been broad enough to enable us to formulate some general rules for conducting geophysical surveys to the best advantage. It is a well established fact that electrical and magnetic methods have aided the geologist to outline bodies of ore, to differentiate between various types of rocks hidden from view and also to determine the thick-ness of the layer of drift that covers the bedrock. Fundamental require-ments for a successful solution of a geophysical problem is the existence of physical differences between the various formations under investiga-tion. If such conditions exist, our problem becomes a physical, mathe-matical and geological analysis of the effects of these differences upon the structure of an arbitrarily produced, or already existing, field of force. Experience has shown that reliable and consistent results in analyzing such fields of force are obtained only if: (1) the methods and apparatus used are scientifically sound and designed to provide information with a maximum amount of accuracy, reliability, sensitivity, simplicity and speed of operation, and (2) the interpretation of the results of such an investigation is guided not only by rigid mathematical rules but also by common sense, based upon sound geological knowledge and imagination. Today, a number of methods are based upon sound principles, are highly sensitive and are well suited for field work. The instrumental developments have resulted in self-contained instruments, which permit the determination of field ratios and intensities with great accuracy. Magnetic surveys have almost become standardized. The electrical methods, mostly based on the determination of potential-drop ratios, or electromagnetic field ratios, are built as bridge circuits and it is easy to determine amplitude, as well as phase relationship of the various electrical and electromagnetic fields.

Jan 1, 1938

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By C. L. Magee, H. W. Paxton

The effects of testing temperature, frorn 77" to 420" K, and volume fraction of martensite on the micro-plastic response of unaged Fe-31Ni martensite-austenite aggregates have been determined. The kinetics of the aging phenomena which lead to a decrease in the microplastic response were also characterized. These determinations, supplemented by other experimental results, show that at least two mechanisms of plastic deformation give rise to the apparent softness of the quenched structures. Only one of these mechanisms is fully discussed in this paper The transformation of retained austenite to martensite during the application of stress leads, in specified conditions, to large microplastic strains. This deformation behavior cannot be described by normal transformation plasticity theory but is shown to result from the fact that stress-assisted formation of martensite is a possible deformation mode. The present results and further considerations of previous work lead to the conclusion that it is unnecessary to postulate a special work-hardening mechanism to explain the mechanical properties of unaged martensite. It is now generally accepted that dislocation motion can occur in many solids at stresses very much below the L'macroscpic" yield stress, e.g., 0.1 pct offset. This phenomenon has been investigated by a variety of techniques including measurements of elastic limit,' effective static elastic modulus,~ and irreversible deformation following stressing at low levels.3"5 Of particular interest to the work to be described are exper -iments conducted on the deformation of martensite in attempts to decide whether freshly quenched ferrous martensites are "hard" or "soft".6 Muir, Averbach, and cohenl and McEvily, Ku, and ~ohnston' have shown that as-quenched ferrous rnartensites can be plastically deformed at relatively low stresses. A difference between these two sets of experiments exists in that some diffusion of carbon would take place before testing in the experiments of Muir et a1. because the plain Fe-C alloys which they have tested transform to martensite well above room temperature. McEvily et a1. examined Fe-Ni-C alloys with Ms of about -30"~ and tested the alloys directly after quenching to — 195" ~ —a technique which obviates any appreciable carbon diffusion. Unfortunately, a characteristic of the alloys which transform below room temperature is that they do not transform entirely to martensite. The results discussed below will show that, because the transformation of this retained austenite under stress leads to plastic deformation, one cannot investigate the properties of martensite by such experiments. The existence of a second deformation phenomenon, which is not caused by retained austenite, is also established in the present work. In line with a previous suggestion,' it is believed that the second microdefor-mation mode is principally due to the internal stresses generated by the formation of martensite. To avoid confusion in the present report, the evidence we have found for this interpretation will be discussed separately in a brief note.7 EXPERIMENTAL Materials. The alloys were induction-melted and cast under vacuum; the resulting compositions are given in Table I. The ingots were hot-swaged to 2-in.-diam bar and further cold-swaged and/or cold-rolled prior to specimen preparation. The standard tensile specimens were machined from sheet. The gage section was 0.05 by 0.2 by 5 in.; 0.75-in.-wide ends had 0.2 5-in. centered holes for pinloading. The three-point bend samples were 0.075-in. thick and 0.6 in. bide. The distance between the outer loading points was 5.5 in. In order to establish a standard starting condition, all specimens were quenched to 77°K prior to annealing in vacuo for austenitizing. The temperature of the austenitizing anneal was controlled to + 5"~. The testing and aging temperatures were maintained by various liquid baths (nitrogen, 77"~; freon, 130° to 200°K; acetone, 200 to 300°K; silicone oil, 300' to 450°K) to better than il°K. Strain Measurement. The results herein were derived from both uniaxial tension and three-point bending experiments. For bending tests, the stresses and strains reported are those corresponding to the maximum fiber values. Normally, because of the small strains involved, very sensitive strain measurements are necessary to make microplastic measurements. However, because of the magnitude of the dilatation and shear involved in the martensitic transformation, the requirements in the present experiments proved to be less rigorous. In most experiments the plastic strain was evaluated by measuring stress relaxation and modulus defects. In this method, specimens are loaded rapidly to some predetermined load on an In-

Jan 1, 1969

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By Margaret Dienes, Karl L. Fetters

IT is recognized that ingot structure is important in determining the quality of finished steel. Such elements of ingot structure as the size, shape and distribution of primary crystals; the size, shape and distribution of shrinkage cavities; the degree and kind of segregation (both macro and micro); the distribution of nonmetallic impurities and gas cavities are each the result of solidification phenomena. These structural features vary with variations in ingot practice: Their control requires a knowledge of their correlation with the variables of ingot practice. The structures of full-sized commercial steel ingots have been studied extensively by the Steel Ingots Committee of the Iron and Steel Institute.1 This work has contributed much to our knowledge of ingot structure and the factors that control it. These investigations of necessity have been limited in scope because of their costliness and the great amount of time required. Studies of the structure of small steel ingots have not been very satisfactory because of the rapid rate of freezing of the ingots. Their structures are thus difficult to resolve and to interpret. Medium sizes of steel ingots in the ranges of 150 to 500 lb. do offer opportunity for study, but their cost also becomes greater and their use less expeditious. Experimental models for the study of steel-ingot structure have been made of nonferrous metals. Gathmann2 used lead-tin alloys and reported that they were satisfactory for determination of the location of the major shrinkage cavities and the "planes of weakness" resulting from the pattern of crystallization. Certain features of mold design have been illustrated by these results. Bezdenezhnihk3 has used copper and aluminum ingots similarly and has shown the effect of mold-wall thickness on the depth of columnar grains. These studies of nonferrous models have been useful, but their results have been limited because the analogy with steel ingots obviously is not a close one. Model wax ingots have also been useful in pointing out important features of mold design. Gathmann4 watched the solidification of wax ingots, through a glass-walled mold, and has reported the effects of mold type on the location of the shrinkage cavities. Segregation was simulated by using a mixture of paraffin and stearine and adding a red dye that on freezing segregated preferentially to the stearine. Brearley5 also used wax models to determine .the effects of some of the principal features of mold design. Carlsson and Hultgren6 used stearic acid to show that the columnar crystals of ingots tend to slope upward progressively from the mold wall toward the center of the ingot. As with the nonferrous ingots, the wax ingots have

Jan 1, 1943

By T. F. Archbold, P. G. McCormick

Silica fiber 11arkevs and hardness irzdentatiozs have been used to study the thermal diffusion of racancies in zinc placed in temperature gradients of 460o and 706oK per Cm All markers mored toward the higher temperatures, and the data show that the heat of trarlsport Q is greater than the eizthalpy of z,acancj3 forrjalion E by an amount equal to 3.5 kcal per mole. These results ore not in agreement with those obtained in either of the two previous studies with zinc. The problem is discussed in terms of experimental differences and racancy source and sink efficiencies. THE general interest in thermal-diffusion phenomena over the past several years has prompted a number of marker movement studies using pure metals. In order to understand better the relationships between thermal and mass flow, a general goal of the experiments has been to obtain values for the net enthalpies carried by the diffusing atoms. For self-diffusion by means of the vacancy mechanism, the determination of relative marker positions before and after an anneal in a temperature gradient permits a calculation of a value for (Q - Ef). Q is the transferred enthalpy, and Ef is the enthalpy of vacancy formation in the metal being investigated. The initial experimental study of thermal diffusion in pure metals was accomplished by Shewmon who found essentially no movement of surface-hardness indentation markers in single and bicrystals of zinc held for 20 days in a temperature gradient of 310°C per

Jan 1, 1967

By A. S. Odeh

This paper analyzes the effect of limited entry to flow at the wellbore on the steady-state productivity of a well. Wells that have been opened to flow along a fraction of their productive interval are termed wells with limited entry. Previous work treated the cases of a partially penetrating well, a well producing from the central portion of the productive interval and a well in which several intervals equally spaced were open to flow. In this paper the open interval can be located anywhere within the productive interval. Thus, in a sense, it generalizes previous work. The finite cosine transform was used to arrive at a solution for steady-state flow of a slightly compressible fluid. The solution was programmed for a CDC 1604 computer. Numerical vaIues for rd = 660 ft, r, = 1/4 ft, and range of sand thickness of 20 to 200 ft are presented in graphical form. The effect of rd and r, values on the result is shown in a table. The correct calculation of skin and damage ratio in the presence of limited entry to flow is explained and illustrated by examples. Moreover, the paper shows how to calculate the net decrease in productivity due to the combined effect of limited entry and perforations. INTRODUCTION In some wells only a fraction of the productive interval is open to flow. Location of this fraction is usually dictated by formation characteristics and reservoir behavior. For instance, if a gas cap exists, the open interval is located away from the gas-oil contact to prevent any possible gas coning. Wells that intentionally have been opened to flow along a fraction of their productive formation are tened wells with limited entry. Obviously, unintentional completions of this type also exist. Limited entry to flow decreases well productivity. Magnitude of the loss depends on the fraction of the formation open to flow, on the thickness of the sand, on the location of the open interval and on the ratio of rd /r, where r , is well radius and rd is the drainage radius of the well. The use of pressure buildup data on producing wells to calculate the condition of the formation around the wellbore is an accepted practice. van Everdingenl and Hurst2 introduced the concept of she skin factor s considered to be due to a thin layer of different permeability immediately around the wellbore. These authors dealt with the case of a well of complete radial geometry, i.e., a well with open-hole completion that completely penetrates the formation. The presence of a low-permeability skin results in a loss of productivity, as does limited entry. Therefore, if pressure buildup data obtained on a well with limited entry are used to establish the presence or absence of skin (i.e., formation damage), and a correction is not made for this loss of productivity, the calculations would result in an erroneous skin value. They might indicate the presence of formation damage when in reality there is none, or they might indicate a value larger than the true value. This could lead to an incorrect basis for planning remedial measures. Muskat3 studied the problem of partially penetrating wells for the case of incompressible flow. He presented equations and figures which allow estimation of loss in productivity. Brons and Marting,4 using equations based on Nisle's work,5 studied the loss of productivity for three cases. The first was for a partially penetrating well; the second was for a well producing from only the central portion of a productive interval; and the third was for a well in which several intervals equally spaced were open to flow. Their work was for steady-state depletion-type reservoirs wherein the well radius of drainage is established and the fluid is considered to be slightly compressible. Considered in this paper is the problem of wells with limited entry in which the open intervals are located anywhere within the productive sand. The finite cosine transform is used to arrive at a

Jan 1, 1969

By W. O. Philbrook, K. M. Goldman, G. Derge

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951

By W. S. N. Waring, E. C. Bain, E. S. Davenport

The more familiar compositions of both the iron-carbon-chromium' and the iron-carbon-tungsten2 systems have been investigated with a degree of thoroughness which has permitted the construction of their three-dimensional equilibrium diagrams; and it is probable that these equilibrium diagrams are sufficiently accurate for the present metallo-graphic needs. Strangely enough, in spite of their importance, the alloys of iron, carbon and manganese apparently have not been investigated in the same systematic manner, and so far as is known, no three-component equilibrium diagram for this system is available. Even iron-carbon-nickel alloys3 have been studied rather more thoroughly; for these the solidus and liquidus surfaces have already been determined, but the solid transformations in this, as in the manganese system, have not been reported systematically. The present paper deals with the constitution at equilibrium of a series of 36 iron-carbon-manganese alloys of commercial purity limited by 1.5 per cent carbon and 15 per cent manganese, a range of compositions including most of the manganese steels. The temperature range of melting has not been determined, nor has the high-temperature (delta iron) ferrite equilibrium been included in the study, it being considered that the more important characteristics of the manganese steels are their ordinary transformations in the solid state. The delta iron region is almost certain to be a small tetrahedron not very different in magnitude or contour from that in the iron-carbon-nickel diagram. It is probably true

Jan 1, 1932

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

TWO recent developments in open hearth steelmaking have had a substantial impact on metallurgical practices and operating procedures. These are: (1) the use of oxygen roof lances for accelerating the refining reactions, and (2) the use of a spring-arch, basic roof for prolonging the life of the furnace. Although these practices can be used separately, they are generally used to complement each other in an effort to obtain minimum heat time consistent with an acceptable rate of wear of the refractory roof, walls and port ends. DECARBONIZATION BY OXYGEN INJECTION The use of oxygen to speed carbon elimination was perceived by Sir Henry Bessmer but its practical use in steelmaking could not be realized until processes were developed for the manufacture of low cost, tonnage oxygen. However, as early as 1922 Bigge1 obtained a patent covering the use of gaseous oxygen to speed decarbonization of a molten steel bath. At that time, oxygen was available only in bottles and at a cost of $240 per net ton. At the end of World War II the price of oxygen had dropped to $80 per net ton, and as a result, metallurgical oxygen (99.5 per cent began to come into widespread experimental use for decarbonization in open hearth and electric furnace shops.2-8 Even this price prevented oxygen's routine use for other than decarbonizing the bath in shops producing substantial quantities of steels containing less than 0.40 per cent carbon. Today, tonnage metallurgical oxygen can be manufactured for less than $15 per net ton, and commercial purity oxygen (95 per cent is reported to cost less than $5 per ton. Thus, it is not at all surprising to find many open hearth shops effectively using large quantities of oxygen to accelerate decarbonization. Equipment for Oxygen Injection. The oxygen may be injected by a lance pipe inserted through the wicket hole and pushed several inches into the steel bath, or by a water-cooled jet inserted through the back- wall, endwall, or roof, and immersed in the slag or set just a few inches above the slag. Oxygen at approximately 100 psi is piped directly to control stations adjacent to each furnace. The installations should include adequate safety devices such as fire checks and emergency valves,

Jan 1, 1964

By Paul Soros

Terminal facilities were recently completed at Conneaut, Ohio, on Lake Erie, for the Bessemer and Erie Railroad Co. (a wholly-owned subsidiary of U.S. Steel Corp.) which may become the blue- print for all future coal shipping terminals. Design and engineering of the new facility was by Soros Associates, New York, N. Y. Unlike terminals of conventional design, for example, those at Toledo and Newport News, which load coal directly from the railroad car to the vessel, the new installation passes the coal into temporary storage, loads the vessel from temporary storage and provides alternative reclaiming systems in case of major system failure.

Jan 1, 1966

By T. L. Joseph

LARGE deposits of manganiferous iron ores, representing several million tons of metallic manganese, occur in the United States. The Minnesota deposits of such ore-are of outstanding importance because of their size, state of development, ease of mining and proximity to the Great Lakes, which permits water transportation to steel centers. In' view of the fact that our steel industry requires large quantities of manganese, for which no satisfactory substitute-has been found, and because our reserves of ferro-grade ore are comparatively small, the development of methods that will make our large deposits of manganiferous iron ores available as a source of ferromanganese is an important problem. Realizing the importance of this problem, some years ago the North Central Station of the U. S. Bureau of Mines and the Minnesota School of Mines Experiment Station undertook jointly the development of methods for recovering the manganese content of manganiferous iron ores in a: form suitable for the production of ferromanganese, the 80 per cent. alloy indispensable in producing steel. Two types of manganiferous iron ores have been described in previous reports. I The brown ores are higher in iron and lower in manganese than the black ores; the black ores are more siliceous but contain less phosphorus. The utilization of the iron content of the brown ores in the production of steel appears to furnish the best basis for their treat-ment. The method of attack has been to work out modifications in iron and steel practice so as to recover manganese in the form of slag comparable to ferro-grade ores. The greater part of the experimental work has been conducted with a 6-ton blast furnace and a Y2-ton basic open hearth. This paper is devoted mainly to open-hearth tests in which high-phosphorus spiegel

Jan 1, 1930

By J. D. Mote, A. Rosen, J. E. Dorn

The effect of strain rate and temperature on the critical resolved shear stress for (1100) [1120] prismatic slip was determined for the intermediate hexagonal phase containing about 67 at. pct Ag and 33 at. pct Al. Whereas the flow stress increased only slightly as the test temperature was first decreased below room temperature, a rapid increase inflow stress was obtained with yet greater decreases in temperature from about 240" to 4°K. The effect of both temperature and strain rate on the flow stress over the low-temperature range could be completely rationalized in terms of the Peierls mechanism when the deformation is controlled by the rate of nucleation of pairs of kinks. A few years ago Mote, Tanaka, and Dorn1 observed that the critical resolved shear stress for prismatic slip of a 67 at. pct Ag plus 33 at. pct A1 hexagonal intermediate phase by the (1100)[1120] mode decreased precipitously as the test temperature was increased from 4" to about 160°K. Their results for both basal and prismatic slip are given in Fig. 1. It is obvious that only the flow stress for prismatic slip is strongly temperature-dependent, whereas the flow stress for basal slip is independent of temperature. If the temperature dependence of the flow stress were primarily due to interstitial impurities, it might be expected that they would influence the flow stress for basal slip as well. Since the activation volume at 115°K for prismatic slip was determined to be about 15b3, where b is the Burgers' vector, this thermally activated deformation process was tentatively ascribed as being due to the Peierls mechanism. But the various analyses of the Peierls mechanism then available as formulated by Seeger2 and also by Lothe and Hirth3 did not agree well with the experimental data. Since that time a more realistic theory for the operation of the Peierls mechanism under conditions where the strain rate is determined by the rate of nucleation of pairs of kinks has been presented by Dorn and Rajnak.4 The present investigation was, therefore, undertaken in order to provide the essential data for a careful check on the agreement between this theory and the low-temperature deformation by prismatid slip of the above-mentioned Ag2A1 intermediate phase. EXPERIMENTAL TECHNIQUE Single-crystal specimens so oriented that the [1120] direction and the normal to the (1100) plane were at 45 * 2 deg to the tensile axis were grown from the congruent melting composition of about Ag2Al for the intermediate hexagonal phase by the

Jan 1, 1964