Search Documents

By C. V. Millikan

Temperature measurement in wells is an old practice and geothermal gradients have been of interest to geologists for many years.le2 Their application to the operation of oil wells is a more recent practice. It has long been recognized that temperature anomalies occur in drilling and producing wells but thermometers that could obtain a satisfactory record of the anomalies were not available. The normal geothermal gradient is con-sidered as being about one degree Fahren-heit for each 60 ft. of depth.4 This "nor-mal " gradient varies in different areas, but whatever it may be in an area there is little variation from the surface to as deep as the : drill penetrates. The normal gradient is appreciably changed by gas expanding ; from the reservoir into the borehole or by the movement of fluid through a borehole : while drilling, producing, or circulating. It is the resulting anomalies and abnormal gradients from which conditions in wells can be interpreted. Some of the applications of such interpretations are locating the position of oil or gas sands, permeable strata in a reservoir zone, gas-oil contact, source of water, casing leaks, and the top of cement behind casing. Thermometers A thermometer for use in wells must be sensitive and have a low thermal lag. The sensitivity should permit recording 0.2OF. or less for differential temperatures although the actual temperature need not be more accurate than 1°F. The thermal lag should be as low as rugged construction will permit in order to allow surveys to be made in a minimum of time. Of the several kinds of thermometers, these requirements are most easily obtained with the vapor-pressure, expansion, and electric-resistance types. Thermometers for use in wells may be self-contained—that is, the complete instrument is lowered into the well and a record made of the temperature—or the thermal element only may be lowered into the well and the temperature recorded at the surface. The vapor-pressure and expansion types are more adaptable for a self-contained instrument while the electric-resistance thermometer is more suitable for surface recording of temperatures. The self-contained instrument can be run against high pressure on a single wire line with only one operator required. The instrument and its hoisting equipment is easily portable and can be mounted on a small car. The disadvantages are a somewhat greater thermal lag and the necessity of completing a run before any temperature or temperature anomaly is known. A surface-recording thermometer has the advantage of being somewhat more sensitive and of having a lower thermal lag. The Operator can see what anomalies are encountered and can immediately change the running conditions of the instrument or the well conditions in order to obtain the most

Jan 1, 1941

By John W. Vanderwilt

THE unpredictable behavior of ground movement and subsidence has complicated the problems that attend the extraction of large quantities of ore. Special studies, particularly relating to coal mining, have yielded such a voluminous literature and so many involved controversial theories that a partial review would be difficult. Limited space makes any kind of a review impractical. The features to be considered cover only a relatively small part of the broad problems of ground movement and subsidence, but it is believed that this small part is critical. The practical aspects are important, since they bear directly on safety of mine workings, on recovery of ore and on dilution of ore in block caving and related systems for extracting large quantities of rock. The ground movement to be described occurs outside the vertical boundaries of a caved block in the area that is commonly referred to as being in the "zone of draw." "Draw" is a term that originated in the subsidence problems related to coal mining, and it is defined by a line drawn from the margin of the area caved underground to the most distant fracture at surface on the same side of the caved area as shown in Fig. I.1 " A line thus drawn is called the cave line, and its angle with respect to the horizontal is the cave angle or angle of draw. It is understood that the line is taken normal to the limit of mining, and in a vertical plane. The prevailing theories as to draw and angle of draw assume that appreciable movement occurred along the cave line, which has been described as a fracture resulting from the shearing action brought about by the weight of the overlying load. Fig. 2 shows diagrammatically the mechanics of ground movement adjacent to an area of subsidence according to the prevailing theory of draw (A, from Royce2) and, for comparison, ground movement observed in the Climax mine (B). The text in Peele's Handbook2 referring to Fig. 2 does not state the meaning of the "original position of top of workable ore" in the rectangular space above "ore in place," and the arrows are not explained. However, this presentation is most concerned with the zones outside the rectangle. According to the prevailing theory, as shown at the extreme left under A, Fig. 2, the vertical tension cracks at surface change at a shallow depth to shear fractures forming the cave line, and it is assumed that appreciable movement takes place along the cave line toward and into the subsiding caved block. The mechanics of ground movement observed in the Climax mine, as shown under B, Fig. 2, does not accord with the prevailing theory, particularly as regards the cave angle and draw. The vertical

Jan 1, 1946

By Y. C. Liu, H. Margolin

Investigation of martensite habit plane in water-quenched Ti-Mn alloys was carried out in the range of manganese contents between 4.35 and 5.25 pct. On the basis of 22 measurements, the poles were observed to fall into two groups, indicating the existence of two habit planes. The Miller indices of the poles close to these two groups were found to be <334>ß and <344>ß. TITANIUM has an allotropic transformation at 882.1° ± 0.5C1 by which the high temperature ß (body-centered cubic) phase changes to a (hexagonal close-packed) phase. It is well known, as in the case of low carbon steel, that the unalloyed high temperature ß phase cannot be retained no matter how rapid the cooling rate. However, the addition of alloying elements usually lowers the transformation temperature continuously and stabilizes the ß phase to a temperature much lower than the allotropic transformation temperature in pure titanium. A typical example of this behavior is found with manganese-alloying of titanium. Fig. 1 shows the titanium-rich Ti-Mn equilibrium diagram as established by Battelle Memorial Institute.&apos; The addition of manganese lowers the ß transus line and the eutectoid reaction takes place at 550°C, the eutectoid composition being 20 wt pct Mn. However, upon quenching to room temperature from the ß field, the ß phase can be completely retained with much less manganese, see Fig. 2. If the composition is less than that required to stabilize the ß phase completely, a plate-like structure, similar to that of martensite in other alloy systems, appears as shown in Fig. 3. Much lower alloying content merely intensifies the amounts of these transformed structures, as shown in Fig. 4. This paper presents the results of an investigation of the habit plane of these martensitic structures in Ti-Mn alloys. Experimental Procedure Investigation of the pole of a given platelet was made using the two-surface method of analysis." In order that a given martensite trace on two surfaces be readily recognized both at low and high magnifications, it is desirable that only a small amount of martensite be present. From a review of the data obtained at Battelle Memorial Institute4 on quench hardening in Ti-Mn alloys and the results of Duwez" on transformation in Ti-MO alloys, it was decided that the most appropriate Ti-Mn composition for this study would be about 6 pct Mn. A group of alloys containing from 3 to 10 pct Mn was made to bracket this composition. The choice of the 6 pct alloy was apparently proper, since it was later learned that approximately 5.5 to 6 pct Mn is required to stabilize the ß phase on water quenching.

Jan 1, 1954

By L. C. Brown, A. J. Stewart

Phase transformations have been studied in Ag-Zn alloys quenched from the high-temperature bcc 0 phase and lying in the composition range 37.4 to 50.0 at. pct Zn. On quenching, the alloy with the lowest zinc content transformed to massive a (fcc); all other alloys formed the ordered (3&apos; phase. On deformation, a martensitic reaction took place forming a close-packed structure. At Lou&apos; zinc contents transformation to this structure was complete. However, above 43 at. pct Zn a p.rogressively increasing amount of ß&apos; was retained following deformation. The close-packed structure was fcc at lower zinc contents (under 47 at. pct Zn) and either hcp or a mixture of fcc and hcp at high zinc concentrations. The structures produced by cold working were unstable and on aging transformed to the ß&apos; phase or the complex hexagonal to phase. For low zinc contents (under 43 at. pct) the fcc st-ructure transformed directly to the equilibrium To phase. With higher zinc contents, some 13&apos; was retained following defownation, and on aging the amount of this phase relative to the close-packed structure increased. On further aging both structures transformed cornpletely to PO. Metallographic examination indicated that the nature of the deformation product depended very markedly on the mode of deformation. Tensile deformation gave a microstructure characteristic of thermal martensite. KING and Massalski1 have shown that an alloy of Ag-50 at. pct Zn quenched from the high-temperature bcc ß phase undergoes a low-temperature ordering reaction forming ß&apos; which can be retained to room temperature. On deformation an hcp phase is produced, although this is unstable and the structure reverts completely to ß&apos; on aging. In the present paper, the work of King and Massalski is extended to cover a wide composition range in the p phase, observations being made of the structure of the quenched 13 and of the effects of deformation and aging. The relevant portion of the Ag-Zn phase diagram is shown in Fig. 1. King and Massalski have shown that close to stoichiometry the ß&apos; phase is the equilibrium structure at low temperatures. The approximate composition range of this phase, taken from a recent paper by Pops and Massalski,3 is shown on the phase diagram. The locations of atom sites are very similar in the ß&apos; and to structures, and the 4, structure can be derived from the 0&apos; structure by a small movement of atoms mainly in the direction of the cube diagonal.4&apos;5 However, the probability of filling any particular atom site by a silver or a zinc atom is markedly different in the two structures. The structure can be considered partly ordered but the arrangement of the ordered atoms is completely different from that in the p&apos; structure and transformation from ß&apos; to requires a large fraction of the atoms to change position. It has been shown that the ß&apos; transformation is thermally activated involving normal nucleation and growth processes.5,8 Massalski and Barrett7 have shown that in the Cu-Zn binary the (3 phase can be retained in the ordered state to room temperature over a wide composition range. On deformation a new close-packed phase is produced, the structure varying from fcc to a mixture of fcc + hcp to hcp alone with increasing zinc concentration. It appears that an ordering reaction is necessary to retain the bcc phase to room temperature. In CU-Ga,8 the bcc phase cannot be retained to low temperatures as it transforms by a massive reaction above the ordering temperature of the ß phase. The structure of the massive phase is very similar to that in Cu-Zn, varying from fcc to fcc + hcp to hcp with increasing zinc concentration. Similar structures have also been observed in CU-A1,9 Ag-Cd,10,11 and Ag-Al.12 EXPERIMENTAL The alloys were prepared by melting fine silver (99.99 pct purity) and electrolytic zinc (99.999 pct

Jan 1, 1969

By A. Kenneth Schellinger

DURING the comminution of a brittle material in the presence of dry air, no known phase change or chemical reaction takes place. The energy changes associated with the comminution are those of the transformation of kinetic energy into heat energy and the energy absorption represented by the actual rupture of molecular and/or ionic bonds. The random nature of the actual grinding process in a tumbling-mill often precludes the effective application of a rupture force on each individual particle of brittle mineral present. The result must be a great deal of useless vibration on an atomic scale in both the brittle mineral and the grinding medium below the elastic limit, which vibration is eventually manifested as heat energy in the mill. The actual rupture of molecular, or ionic, bonds creates new surface on the brittle minerals; each square centimeter of this new surface then must possess a number of potential bonds, each of which could reform theoretically with the release of energy. The sum total of this potential energy of bonding per unit of new surface, minus bond satiation effects of the enclosing gas or liquid, must be the surface energy of the mineral. If the comminution of the brittle mineral were carried out within the chamber of a calorimeter, the energy released as heat could be determined rather accurately. Moreover, the total kinetic energy input to the comminuting mass (mineral and medium) conceivably could be derived by a suitable torquemeter and revolution counter if the whole calorimeter were revolved. The difference between these two energy figures should then represent the net energy (gross energy input—heat enerb output) used in creating new surface, gliding or slip on atomic planes, twinning, and possibly other lattice rearrangements within the mineral. If it be postulated further that with a hard, brittle crystalline material, such as quartz, the energy used to produce gliding, twinning, and other permanent lattice movements is a very small fraction of the total net energy absorbed, then this energy absorption within the grinding calorimeter can be ascribed to the creation of new surface energy alone. Such energy is, from the thermody-namic standpoint, the true effective work of the grinding device, in this case a tumbling-medium mill. The ratio of this effective work (in calories) to the total energy input (in calories) should express the thermodynamic efficiency of the comminution taking place under the conditions used in the grinding calorimeter. This approach to the measurement of the energetics of tumbling-mill grinding was suggested by some previous work by Fahrenwald and coworkers&apos; with a laboratory ball mill and a thermometer. They measured the efficiency of grinding based on the formula: Pct Grinding Efficiency = Energy (calories) — Thermal Energy x 100 1npZ Output (calories) Energy input (calories) Efficiencies thus measured, while grinding quartz sand, ranged from 19.7 pct to 7.4 pct. Cook in 1915,&apos; used this approach to the problem of grinding efficiencies in stamp batteries and obtained the energy input by stamp weights times drop distances and the energy output by means of thermometers and pulp flow rates. He calculated that 80 pct of the input energy to the stamp shoes was wasted as sensible heat in the ore pulp. No other studies of comminution by this method of energy differences came to the author&apos;s attention. Reasonable agreement as to the order-of-mag-nitude of comminution efficiencies in tumbling-media mills is lacking in the literature. There is a widespread impression among technical workers that the grinding efficiency of the industrial ball mill may be on the order of 1 pct, or even a fraction

Jan 1, 1952

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By J. J. Taber

The turbulent flow drag coefficients, or friction factors, have been experimentally determined for the cut-tings normally encountered in drilling operations. The gas law and average drag coefficients for characteristically flat particles (limestones and Shales) and for angular to sub-rounded particles (sandstones) were used to extend Newton&apos;s equation to a more useful form. The resulting equations are expressions for the slip velocity of a particle as a function of the particle size and shape, the bottom-hole injection Pressure, and the Bottom-hole temperature. The velocities necessary to lift actual rock cuttings as observed in the laboratory were compared with velocities predicted from the derived equations. Results indicate that there is no single correct circulating velocity and that the commonly used 3,000 ft/min linear velocity may he sufficient to lift only very mall particles. The advantage, in terms of horsepower requirements, of cycling high pressure air to obtain lower compression ratios was shown. INTRODUCTION A promising departure from standard rotary hydraulic drilling is air or gas drilling. In many instances the rate of penetration and bit life increases resulting from this method have been very substantial. Further the application of air drilling in areas of lost circulation or water sensitive pay zones has been highly successful. Purpose For the drilling contractor, the practical question remains, "How much air pressure and volume should I have?&apos; lt is necessary to have a reasonable knowledge of the air velocities and pressures required in air drilling operations for the proper design and most advantageous use of surface equipment and for adequate removal of cuttings from the borehole. Eased on experience, most operators agree that at least 3,000 ft/min linear velocity is necessary for satisfactory hole cleaning.&apos; It was the purpose of this investigation to evaluate the drag coefficients, or friction factors, for the cuttings normally encountered in drilling operations, i.e., sandstones, limestones and shales, and to utilize the values obtained to develop an expression for the minimum velocities and pressures (hence the volumes) necessary to lift these cuttings. THEORY Several investigators have done extensive work on the ability of drilling mud to lift bit cuttings. They conclude that the ability of a drilling mud to lift cuttings is dependent on the density difference between the rock being drilled and the drilling mud, the cutting size and shape, the mud flow constants, and the flow state (laminar, transitional or turbulent) of the mud. However, drilling muds are not true fluids but have a variation of viscosity with velocity in laminar flow and a constant apparent viscosity in turbulent flow. A survey of the literature revealed that no experimental work had been done to determine the velocities necessary to lift actual rock cuttings using a compressible fluid such as air or gas. In 1953, Nicolson6 stated that in air drilling fluid mechanics the particles could be assumed spherical in shape and that ; constant drag coefficient of 0.5 could be used due to the highly turbulent flow of the circulating air. By equating the turbulent resistance on the particle to the gravitational force on the particle, he obtained the expression, ^ = 2.67^y ,.......(1) where V, is slip velocity of spherical particle, ft/sec; D is particle diameter, in.; p, is particle density, 1b/ft8; and p, is fluid density, lb/ft3. However, as stated earlier, most operators seem to agree that adequate hole cleaning can be obtained by circulating a sufficient volume of air to give a linear velocity of 3,000 ft/rnin in the annular space. Basic Equation The velocity with which a solid particle freely falls through a fluid will increase until the accelerating force, gravity, is equal to the resisting forces, buoyancy due to the fluid displaced by the particle and friction due to the relative motion of the particle through the fluid. When the accelerating and resisting forces become equal,

By John W. Cahn, David A. Karlyn, Morris Cohen

The massive B(bcc) — am (fcc) transformation in Cu-Zn alloys has been studied isothermally by pulse-heating the retained ß phase from room temperature to the reaction temperatures. The transformation is found to occur only in the single-phase a region of the equilibrium diagram. The massive growth rate is of the order of 1 cm per sec and is constant at each temperature, usually after a delay time of some milliseconds. The delay time depends on the reaction temperature in C-curve fashion, while the growth rate increases monotonically with temperature over the single-phase range. The absence of isothermal massive transformation in the two-phase region does not arise from slow growth rates at such temperatures, but because the reaction cannot get started there. It is proposed that the massive transjormation initiates at small preexisting a particles which have rejected zinc into the surrounding 0 matrix. Only within the single-phase region can these particles consume the excess zinc during diffusion-controlled growth and thereby accelerate to the steady-state massive growth rate. The onset of massive growth marks the end of the delay time, and the growth rate then becomes interface-controlled. These isothermal transformation characteristics explain why the usual composition range for massive-kinetic studies by quenching is so limited. The same principles can be extended to more complex alloy systems by recognizing that the single-phase region in which the massive transformation can occur may not be stable with respect to phases not participating in the reaction. MASSWE transformations are now recognized as a regular class of solid-state reactions involving no compositional change (like martensitic transformations) and no shear displacements (unlike martensitic transformations). The name was first coined by Greninger1 in 1939 to describe the coarse grains of fcc a solid solution generated via a fast reaction from the parent bcc 0 solid solution in Cu-A1 alloys. However, some 9 years earlier, phillips2 had already described a similar transformation in the Cu-Zn system. The fact that the massive a formed as a single phase during drastic quenching from the 0 region of the equilibrium diagram signified that compositional changes were precluded. and the reaction was presumed to take place as in a one-component polymorphic transition by nucleation and growth. Phillips also observed that the occurrence of the massive transformation in the Cu-Zn system was extremely sensitive to alloy composition. For example. in a Cu-37.3 at. pct Zn alloy. the ß — am (am = massive transformation product) reaction was found to predominate and was not suppressed by iced-brine quenching from the 0 region. whereas at compositions greater than 38.3 at. pct Zn the massive reaction did not appear at all. Knowledge concerning massive transformations has bee11 substantially enhanced over the years by Massalski and his coworkers; an excellent summary of his papers and the current understanding of this type of reaction has been published recently by Barrett and ~assalski." he massive transformation product grows in roughly nodular form. often with irregular boundaries but sometimes with almost planar interfaces. The latter may have simple crys-tallographic indices relative to the 0 matrix. or the indices may be complex just as in the case of mar-tensites.&apos;1 Little is known about the existence of orientation relationships between the massive and parent phases. A striking feature of massive transformations is that the massive units start almost exclusively at grain boundaries of the parent phase and frequently propagate on a broad front across matrix grains and grain boundaries of various orientations. Because of the rapid growth rate, it is thought that the interface motion is controlled. not by long-range diffusion. but by thermally activated atom jumps across the transformation boundary.

Jan 1, 1970

By W. A. Backofen, N. E. Paton

DEFORMATION twinning contributes to the plasticity of titanium and has been reported on {10i2}, {1121},{11221}, {1123}, and {1124} planes.&apos; Twinning on {1011} has also been reported in commercially pure titanium as a result of quenching from 1000&apos;, but no reports of such twins occurring as a result of deformation alone are known to the authors. In this study single crystals grown from iodide titanium were compressed parallel to the c axis over the temperature range 25 to 800°C. From it has come evidence that (10il) deformation twins are the most common type between 400" and 800°C. Crystals about 6 mm high with a rectangular cross section measuring about 3 by 4 mm were used in the tests. Chemical analyses showed them to contain 220 to 250 ppm 0 arid 10 to 15 ppm N. The long axes of the crystals were made parallel to the c axis while the sides were parallel to (i100) and (1120), as shown in Fig. 1. The crystals were compressed between polished alumina platens with no lubrication, in a vacuum of 2 x lom5 torr. Between 25&apos; and 300°C the predominant twinning mode was (11221, which is to be expected for this stress state. There was an abrupt change at 400°C, however, and from that temperature up to 800°C twinning took place almost entirely on (10i1 ). Twin planes were determined by the two-surface rnethd. Measurement of the crystal orientation within several (10i1) twins by means of polarized-light4 and transmission electron microscopy showed that the lattice reorientations were the same as those previously reported for the (10i l ) twinning in magnesium.&apos; This reorientation is consistent with The calculated (10il ) twinning shear for titanium is 0.10, while that measured from surface offsets on a (1150) face, which is parallel to the shear direction, was about 0.15. Slip within the twins, or in the matrix adjacent to the twins, probably accounts for the larger measurement. Slip in both locations was judged to have occurred from observations on foils in the electron microscope.

Jan 1, 1970

By Charles Catlett

My attention having been called several years ago to the possibility of increasing the yield of coke per ton of coal, as obtained in certain bee-hive ovens, I called the attention of the Institute to the matter at the New York meeting in 1899. I have had occasion since to witness the indifference with which this matter is ordinarily considered, and, on the other hand, the marked improvement which comes from even a most perfunctory effort in that direction; and I am almost tempted to say that nothing in connection with the coking of coal is at present so important. There are other factors, which are fundamental and necessary; but they have been considered already ; while the question of yield is, as a rule, absolutely ignored, or some figure is taken as the result of a special burning of one or two ovens, and the assumption is made that the whole battery is yielding at that rate. The uncertainty of this assumption I may illustrate by saying that, in my own observation, the burning of a single oven in a battery frequently gives, by actual weight, as much as 69 or 70 per cent. of merchantable coke, while the battery as a whole was yielding only an average of 63 per cent. Only from careful records, checked at least once a month, of the weight of the coal going to the ovens and the weight of coke produced, can any correct idea of the actual yield be gained, or methods be modified so as to produce good results; yet, as a rule, the crudest estimates are usually the only available data. In many cases there are reasons for this loose practice. The coal is mined by measurement; the payment for drawing the ovens is in proportion to the amount of cod which goes to them; and, not uncommonly, the royalty is so much a ton of coke, not of coal. The mine-manager is tempted to increase the volume of coal mined which is paid for as a ton, and to do the same thing in charging the ovens. Nor does he

Jan 1, 1903

By C. E. Agnew

THE Eastern district, composed of New Jersey and eastern Pennsyl-vania, with its native ores, was the cradle of the iron industry of the United States. The district attained and held the leadership in produc-tion of pig iron for over 100 years, from pre-Revolutionary days to approximately 1875. The first shipment of Lake hematite ore was made in 1853. It was a small shipment, transported by a sailing vessel and a canal barge, but it was the beginning of the end of the supremacy of the Eastern district, although at that time the ore was supposed to be too rich to be successfully smelted with the block coal then in use at western furnaces. The iron made from the first shipment of Lake ore was worked into nails by the Sharon Iron Co., at Sharon, Pa. The writer&apos;s great-grandfather, David Agnew, and his brother, John P., Agnew, owners and-operators of the Sharpsville furnace, Sharpsville, Pa., worked the shipment through a furnace. Because of this, the writer feels some satisfaction in having been one of a group that solved the problem of making profitable an operation using Eastern district ores exclusively. With the development of Lake mines, and the production and use of coke, the Middle West district gradually assumed the position of leader-ship in production; because, even though the ores were transported 1000 miles by water and rail, its cost figure on pig iron was better than that of the eastern producer whose furnace was next to his mine. Such a cost figure was possible because the ore was naturally rich in iron and reduced easily. It was possible to carry a heavy burden on the furnace, which resulted in large tonnage and low coke per ton of iron. This paper is in no sense a technical one. The purpose is to show that with the proper physical preparation of the Eastern magnetites they will reduce as easily as the Lake hematites, and because of the high iron concentration give the Eastern producer just as much advantage as formally he was at a disadvantage in comparison with the Middle West producer.

Jan 1, 1938

By C. E. Agnew

THE Eastern district, composed of New Jersey and eastern Pennsylvania, with its native ores, was the cradle of the iron industry of the United States The district attained and held the leadership in production of pig iron for over 100 years, from pre-Revolutionary days to approximately 1875 The first shipment of Lake hematite ore was made in 1853 It was a small shipment, transported by a sailing vessel and a canal barge, but it was the beginning of the end of the supremacy of the Eastern district, although at that time the ore was supposed to be too rich to be successfully smelted with the block coal then in use at western furnaces The iron made from the first shipment of Lake ore was worked into nails by the Sharon Iron Co , at Sharon, Pa The writer&apos;s great-grandfather, David Agnew, and his brother, John P Agnew, owners and operators of the Sharpsville furnace, Sharpsville, Pa , worked the shipment through a furnace Because of this, the writer feels some satisfaction in having been one of a group that solved the problem of making profitable an operation using Eastern district ores exclusively With the development of Lake mines, and the production and use of coke, the Middle West district gradually assumed the position of leadership in production, because, even though the ores were transported 1000 miles by water and rail, its cost figure on pig iron was better than that of the eastern producer whose furnace was next to his mine Such a cost figure was possible because the ore was naturally rich in iron and reduced easily It was possible to carry a heavy burden on the furnace, which resulted in large tonnage and low coke per ton of iron This paper is in no sense a technical one The purpose is to show that with the proper physical preparation of the Eastern magnetites they will reduce as easily as the Lake hematites, and because of the high iron concentration give the Eastern producer just as much advantage as formally he was at a disadvantage in comparison with the Middle West producer

Jan 1, 1938

By H. L. Luo, P. Duwez, C. C. Chao

BY rapidly cooling alloys from the liquid state, it is possible to obtain solid solutions beyond the equilibrium concentrations, provided that the components are miscible in the liquid state. Typical such cases include CU-Ag,1 Pt-Ag,2 CU-Rh,3 nickel-base alloys with silicon, germanium, and tin,4 and cobalt-base alloys with silicon, germanium, tin, aluminum, and gallium.5 In the present note it is shown that terminal solid solutions can be appreciably extended in A1-Mg alloys. The alloys whose compositions are given in Table I were prepared by induction melting in tantalum crucibles under an argon atmosphere. Both aluminum and magnesium were 99.99 pct pure. Weight losses after melting were less than 0.2 pct for the aluminum-rich alloys and less than 0.4 pct for the magnesium-rich alloys. From these weight losses it was estimated that the compositions of the ingots after melting were accurate within 0.3 at. pct for aluminum-rich alloys and within 0.5 at. pct for magnesium-rich alloys. As indicated in Table I, the compound AuCd10 in which there is an ionic contribution to the bonding. The authors thank Dr. J. H. Westbrook of the Research Laboratory, General Electric Co., for arranging the supply of materials and for his interest. This investigation was supported by the U.S. Atomic Energy Commission under Contract AT(30-1)-1002, Scope I. some of the alloys were also chemically analyzed and the results confirmed the limits of uncertainty based on weight losses. Rapid quenching from the liquid state was achieved by techniques previously described.8,7 The principle of these techniques consists of propelling a small globule of liquid alloy (about 20 mg) onto a copper substrate. The thin foils easily detached from the copper substrate were analyzed by X-ray diffraction using a Debye-Scherrer camera 114.6 mm in diameter and either nickel-filtered copper Ka or iron-filtered cobalt Ka radiation. Since the back-reflection doublets were resolved, the wavelengths used in the computatioas were CuKal = 1.54050A and CoKa1= 1.78892A. Lattice parameters were obtained by extrapolation of the Nelson-Riley function, and the tables compiled

Jan 1, 1964

By Yap Chu-Phay

IN 1923, when the writer began his studies in metallurgy, he came upon an article by Professor Honda on the, Equilibrium Diagram of the Iron-carbon System, 1 which made a profound impression on him. What interested him most was this sentence: "In the recent diagram of the iron-carbon system, the solidus is usually shown as a curve bending considerably downward. But it can be shown by thermodynamics that if the liquidus is straight or slightly curved, the same must also be true for the solidus. Hence, in my constitutional diagram, the lower portion of the solidus is slightly bent upward." Ever since then the writer has been interested in thermodynamics, especially chemical thermodynamics. The applications of thermo-dynamics to the metallic systems have been, in the writer&apos;s opinion, sadly neglected, although we continually use the phase rule in our study of equilibria in the liquid and solid states of metallic alloys. Many investigators, among whom may be mentioned Heycock and Neville, and s Honda and his coworkers, have applied the simple Raoult-van&apos;t Hoff law of depression of freezing point, mainly to determine the heat of fusion, but no attempt has been made to investigate the applicability of the thermo-dynamic laws of solution (as opposed to the laws of solution derived from other sources) to metallic systems" showing either limited or complete solid solutions. Perhaps the reason for this neglect is that until recently there have been so few reliable data on the solidus, which is much more difficult to determine than the liquidus. The writer has under way at the present time an investigation of a number of systems, the solidi of which have been more or less reliably determined. Recently, the writer has not only shown the valid applicability of the thermodynamic laws of solution as applied to the system antimony-bismuth but has also suggested a method of attacking problems involving complete and incomplete equilibria.2 In the present paper, the same method of approach is employed. For convenience, we shall divide this paper into two parts:

Jan 1, 1931

By Walter Herd

FoR the past eight years No. 2 mine of the Cumberland Railway & Coal CO., Springhill, Nova Scotia—a subsidiary of the Dominion Coal Co., Ltd.—has had an unenviable reputation for bumps. As the workings extended in certain directions under a greater cover, these bumps increased in severity and it became apparent that some change in the system of extraction was necessary if the mine was to continue to operate. In September, 1924, following several fatalities resulting from bumps, the Mines Department of Nova Scotia requested from the U. S. Bureau of Mines the services of George S. Rice, Chief Mining Engineer of the Bureau, to report on the conditions then prevalent in No. 2 mine, Springhill. This request was promptly and courteously granted. Mr. Rice made a full investigation and a comprehensive and helpful report, which is embodied in the 1924 Annual Report of the Department of Public Works and Mines, Nova Scotia. Prior to 1925, the room and pillar method was employed and in January of that year (there being a cessation of work from March to August due to labor troubles) longwall retreating on the west side, on a limited scale, and in a small section on the east side of the mine was started. The major portion of the east side was not operated on this system till August, 1926, as there was developed a considerable area ready for pillar extraction between an arbitrary boundary and a point up to which bumps of any consequence had not been experienced. In the interval development work for longwall retreating below the 5900-ft. level was vigorously pushed. This longwall retreating system was suggested by Mr. Rice as a possible remedy and was heartily endorsed by the company officials. This paper describes the conditions and happenings subsequent to Mr. Rice&apos;s report and more especially the results with the longwall retreating system of mining under the peculiar circumstances pertaining to mining No. 2 Seam, Springhill, at depth, and records the conclusions which experience with several severe bumps under this mode of extraction would suggest. Except where necessary to make the paper intelligible as an entity any duplication of Mr. Rice&apos;s report will be avoided.

Jan 1, 1930

By Byron W. Cheever

In working up the process which I described at the Chicago Meeting, May, 1884 (p. 163 of the present volume), for the estimation of phosphorus in iron and steel, I employed samples of steel obtained from one works only, and of a given brand. Since then I have had frequent occasion to test the process on other steels, and find that it works equally well. But some steels present certain colors which may mislead the operator; and I therefore propose a slight change in the directions formerly given. On the second page of my paper, in the second paragraph, I would substitute the following modified directions: Place the flask under the hydrant, till the solution is perfectly cold ; then add, gradually, strong ammonia, with constant stirring, till the solution is changed into a pasty mass and the ammonia is in slight excess; then add cautiously HNO3 (1.40 specific gravity)

Jan 1, 1885

In one of the largest dredging projects of its kind, Lake Asbestos of Quebec Ltd. is stripping overlying mud and sand from the bed of a lake to reach asbestos orebodies 70 to 200 ft below surface. Black Lake, about two miles long by half a mile wide, was almost overlooked in the search for asbestos in Quebec&apos;s ore-rich eastern townships-a search that has been underway there ever since the first asbestos was mined in 1877. Not until 1948 was the Black Lake mineral discovered. Four years later careful exploration was carried out by American Smelting & Refining Co., parent firm of Lake Asbestos. The search involved more than 75,000 ft of diamond drilling and about 5000 ft of underground work. ASARCO, in its first asbestos mining project, decided to proceed with a dredging and draining program to prepare for open pit mining.

Oct 1, 1956

By H. N. Treaftis, J. W. Cahn

THE previous determinations of the solvus of tin in solid lead disagree with one another by as much as 40°C or almost 10 at. pct. Even determinations that appear to be careful differ considerably in both the solubility and its temperature coefficient. Recent kinetic workl -3 on the rate of precipitation of tin from lead-tin alloys and thermodynamic work4 on the heat of solution of tin in lead have given some insight into the time necessary to reach equilibrium in this system. As this time is longer than that used in almost all previous determinations of the solvus, these determinations are questionable. Since the interpretation of recent kinetic results requires accurate values of the equilibrium solubility the present work was undertaken. DISCUSSION OF PREVIOUS RESULTS The methods used in previous studies may be placed into three classes: 1) Several alloys covering a range of compositions are allowed to reach "equilibrium" at a certain temperature.5-7 Some property, such as the X-ray lattice parameter of the lead-rich phase or the re- sistivity of the alloy, is then measured as a function of composition. The solubility limit for that temperature is taken to be that composition at which a discontinuity in the property occurs. However, the recent kinetic work has shown that tin precipitates in two stages. The first stage is rapid but leaves the lead still supersaturated. The second stage is very slow, and it seems from the equilibration times quoted by the investigators of the solvus that the end of the first stage of precipitation was usually mistaken for equilibrium. This is especially true at temperatures below 100°C where the first reaction is still quite rapid (from minutes to months), but where the second stage is so slow that very long holding times are required to reach equilibrium. Alternatively micrographic work8 on several alloys of different compositions seems to have given good results if done carefully. 2) The beginning of precipitation in a homogenized alloy is measured as it cools slowly8-10. Since reactions in solids undercool easily, such determinations will always give too low a temperature for the solvus. 3) Some property of an alloy is measured as a function of temperature while the alloy is above the solvus.5,9,11 The range of temperature can usually be extended slightly into the two phase region. Then the alloy is precipitated at a much lower temperature and slowly reheated. The solvus is taken to be the lowest temperature where the property of the reheated alloy is equal to that previously determined for the homogeneous alloy. Usually one also expects a discontinuity at the solvus in the temperature variation of the property for the reheated alloy. The difficulty in this method is the sluggishness of the dissolution process, and this method may give too high a solvus temperature. EXPERIMENTAL The phase boundary or solvus temperature was determined by a modification of method 3 for a series of chemically analyzed high-purity alloys, ranging from 5.1 to 26.4 at. pct Sn. The resistance, as a function of temperature, of a sample of homogenized alloy (which could easily be undercooled) was compared with the equilibrium resistance which that alloy sample attained after precipitation at room temperature followed by long isothermal anneals at various temperatures. Before each anneal the sample was rehomogenized and reprecipitated. The solvus temperature could be located to within 1°C as the intersection of the resistance vs temperature curves for the homogenized and equilibrium alloys. No attempt was made to locate the phase boundary more accurately since the limiting factor was the precision with which the alloys could be analyzed. This precision was ±0.1 wt pct Sn and corresponds to an error of 1 deg in temperature. This use of isothermal anneals differs from some of the previous investigations in which method 3 was used with baths of slowly rising temperatures. It was found early in the investigation that solvus temperatures tended to be high if the latter method was used even at extremely slow heating rates. For example a

Jan 1, 1961

By J. O. Edstrom, G. Bitsianes

Parabolic rate constants were determined for the formation of wiistite by the solid state reaction between magnetite and iron. The reaction was diffusion controlled and inert marker studies indicated that the mass transport through the wiistite layer was accomplished by means of iron migration. Relationships between rate constants and self-diffusivities are discussed. The transport capacity for iron through dense wustite layers was found to be sufficient to carry on reduction, even in gaseous reduction processes. REDUCTION of iron oxides has been the subject of many investigations. Most of the work, however, has been done on rather crude material and there have been difficulties in correlating the data on a quantitative basis. The reverse process of the oxidation of iron has been studied more thoroughly and usually by starting from the pure metal. As a result, the mechanisms of oxidation are now fairly well known.It has generally been found that the oxidation of metals follows the so-called parabolic 1aw;Q hat is, when the oxides are formed as dense layers, their thicknesses are proportional to the square root of the reaction time. This parabolic law follows directly from Fick&apos;s first law of diffusion The flux, J, is defined as the quantity of diffusing substance passing per unit time through unit area of a plane at right angles to the direction of diffusion. This flux is proportional to the concentration gradient of the diffusing substance, and the factor D, known as the diffusion coefficient, is introduced as the proportionality factor with dimensions of (length)&apos;/time. If the flux is measured as the increase of thickness of the oxide layer (Ax) per unit time (t) and the assumption is made that the concentrations of the reactants at the phase boundaries of the layer are independent of time, Eq. 1 reduces to Integration of this expression yields the parabolic function ax = k . t. [31 The product of the diffusion coefficient and the concentration difference across the oxide layer is included in the constant k. When iron is exposed to a highly oxidizing atmosphere, the oxide phases are formed normally in a topochemical fashion, i.e., the interfaces between the phases maintain parallel positions to the original surface of the specimen. Above 570°C, the phases are orientated usually in the order of iron, wiistite, magnetite, and hematite, a condition in conformance with the requirements of the Fe-0 system. Below 570°C, the wiistite phase is unstable and has not been found as a normal constituent in the oxidation products of iron. There is a strong probability that continuous layers of the solid oxides are formed as the specific volumes of the phases increase in direct order from iron to hematite.&apos; , &apos; Regarding mass transport through dense solid oxide layers, Wagner&apos; has postulated that diffusion in oxides generally may be interpreted as migration processes of ions and electrons. There must be normally a concentration gradient across the growing oxide layer for diffusion to occur. This condition requires that there be deviations from the ideal stoi-chiometric composition of the oxide and accordingly deviations from the strict order of an ideal lattice. Such "lattice defects" include interstitial ions, cation and anion vacancies, quasi-free electrons, and electron holes and are decisive for all migration processes.&apos; Cations, anions, and electrons all may have some mobility in the oxides but the movement of one of the particles generally far exceeds that of the others. Previous work&apos;, 1,2,7 has shown that during the oxidation of iron the migration through the wiistite layer, and probably also the magnetite layer, is confined to the movement of iron ions. Migration through hematite, however, has been found to take place by oxide ion movement. These behaviors are in direct agreement with the type of vacancies present in the respective oxides. Reduction of Iron Oxides The gaseous reduction of iron oxides, like the oxidation of iron, takes place in a topochemical fashion at distinct interfaces between the appearing phases."-&apos;" Porosities might be expected in these reaction products, since their specific volumes are less than that of the starting material. Frank and van Der Merwe" have shown, however, that it is theoretically possible for nonporous layers to form if the degree of misfit in specific volume is less than about 15 pct. These aspects on porosity formation

Jan 1, 1956

By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß&apos;-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,&apos; alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0&apos; phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967