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By T. B. Massalski, H. W. King

An hcp phase may be induced by cold working the ß&apos; phase of the Ag-Zn system. This phase reverts to ß&apos; on subsequent aging. No phase change occurs on cold working the o phase, but ß&apos; is formed when the deformed alloy is subsequently aged at room temperature. It is concluded that for alloys near 50 at pct Zn the ordered bcc ß&apos; phase is the equilibrium structure at room temperature. WhEN the disordered bcc ß phase of the Ag-Zn system is cooled to temperatures below 258o to 274oC, it transforms to a complex hexagonal phase <o.1,2 The nature of the o ß=o transformation has been the subject of some discussion,2&apos;3 and the structure of o has been described in detail.&apos; The latter phase appears to be stable on aging at room temperature but decomposes following cold work. When alloys containing approximately 50 at. pct Zn are rapidly quenched from the 0 phase field, the ß ? o transformation may be suppressed; but the ß phase undergoes an ordering reaction (ß ? ß&apos;). The ß&apos; structure may also be obtained as a result of cold working and aging at room temperature.4 Kitchingman, Hall, and Buckley4 have suggested that the decomposition of (o following cold work proceeds in two stages, (o ? ß followed by ß ? ß&apos;, but did not confirm this by experiment. When the ordered &apos; phases in the systems Cu-Zn5 and Ag-Cd6 are cold worked, they become unstable and transform to a close-packed hexagonal phase (( ) indicating that when order is destroyed in a ß&apos; structure the close-packed hexagonal phase may in many cases be more stable. It thus became of interest to study more closely the effect of cold work and annealing on the stability of both the ß&apos; and o phases in a Ag-50 at. pct Zn alloy. Predetermined weights of spectroscopically-pure Ag and Zn, supplied by Johnson and Matthey, were melted and cast under 1/2 atm of He in transparent vycor tubing. The ingot was homogenized for 1 week at 630°C and quenched into iced brine. Since mechanical polishing was found to induce a phase change, sections were first polished at room temperature, sealed in tubes under 1/2 atm of He, reannealed for several days at 630o or 200°C and then quenched into iced brine. Sections of the alloy thus prepared were found to be homogeneous when examined under the microscope. The sample quenched from 630°C (ß -phase region) was pink in color, whereas the sample quenched from 200°C (o-phase region) was silver. The latter sample showed the characteristic hexagonal anisotropy when examined under polarized light. Filings of the alloy were examined at room temperature, after various heat treatments, using an RCA-Siemens Crystalloflex IV diffractometer with filtered CuKa radiation. The X-ray reflections from flat powder specimens quenched from 630o and 200°C and sieved through 230 mesh were recorded graphically at a scanning speed of 1/2 deg per min. The resultant patterns are shown in Figs. 1(a) and 1(b) and may be identified as those of the 8&apos; and <02 structures respectively. The lattice parameter of the ß&apos; phase was determined as 3.1566Å.* This value compares very well withthatto be expected for a 50 at. pct Zn alloy from the data of Owen and Edmunds? and indicates that no loss of Zn occurred during casting. In order to study the effect of cold work upon the ß&apos; and o phases, filings made at room temperature and sieved through 230 mesh were mounted immediately in the diffractometer-i.e., without a strain-relief anneal. Changes in structure on subsequent aging were followed by scanning repeatedly over the regions of the low index reflections of the ß&apos; and o structures-i.e. , 28 from 35 to 44 deg. Immediately after filing the 8&apos; specimen, additional diffraction peaks were observed in the low-index region of the pattern, as shown in Fig. 1(c). These additional peaks do not coincide with those of the o structure, Fig. l(b), but may be indexed as the (10.0), (00.2), and (10.1) reflections of an hcp phase (<) with nearly ideal axial ratio. However, this hexagonal phase appears to be very unstable since within a very short time at room temperature it reverts back to the ordered ß&apos; phase, the reversion being complete within seven hours. The 5 ? ß&apos; reversion reaction is, therefore, very similar to those already reported in Cu-Zn5 and Ag-Cd6 7&apos;alloys. The action of filing caused the deformed surface of the originally pink ingot to become silver in color, indi-cating that the ( phase possesses similar reflecting properties to the o phase. Hence, the subsequent

Jan 1, 1962

By Martin F. Littmann

Inclusions of MnS and Fe3C have been introduced into single crystals of 3 pct Si-Fe to study their effects on recrystallization behavior and textures after cold rolling and annealing. The presence of MnS in (110) [001] and (111)[112] crystals inhibited primary grain growth and promoted secondary recrystallization but did not alter the texture significantly after annealing at 1200°C. The presence of Fe3C in (llO)[OOl] and (100)[001] crystals caused a refinement of the primary re crystallized grain size but did not promote secondary recrystallization. THE texture behavior of single crystals of 3 pct Si-Fe during deformation and recrystallization has been studied by numerous investigators. The early work of Dunn&apos; followed by Decker and Harker2 involved relatively small cold reductions. More detailed studies of Dunn3&apos;4 and of Dunn and Koh5&apos;6 involved a reduction of 70 pct and recrystallization at 980°C for several crystals. Walter and Hibbard7 studied a greater variety of initial orientations and sought to relate the textures to those of polycrystalline material. Attention was focused on the nucleation process during early stages of annealing and on surface energy effects in studies by Walter and Dunn8 and by HU.9&apos;10 One of the most extensive investigations has been reported by T. Taoka, E. Furubayashi, and S. Takeuchi.11 Most of this work has been conducted using relatively pure crystals with minimal amounts of precipi-tate-forming elements such as carbon, oxygen, sulfur, and nitrogen. Recently, however, S. Taguchi and A. Sakakura have observed that AIN precipitates can alter the recrystallization textures of rolled (100)[001] crystals.12 The present studies were initiated to determine effects of MnS and Fe3C precipitates on recrystalli-zation and grain growth behavior of rolled single-crystals of 3 pct Si-Fe. Both of these types of inclusions play significant roles in the recrystallization behavior leading to the formation of the (110)[001] or cube-on-edge texture in commercial grain-oriented silicon iron. It is well known that (110)[001] primary grains are formed by recrystallization of (110)[001] or (11 l)[ 112] crystals after cold reduction of about 60 pct or more. Crystals of these orientations, therefore, were selected for study of the effect of MnS in-clusions on grain growth. On the other hand, a major component of the texture of cold-rolled, polycrystal-line 3 pct Si-Fe is the (100)[011] orientation. The function of Fe3,C inclusions is of interest for this orientation. EXPERIMENTAL PROCEDURE The single crystals used are listed in Table I and were obtained from commercial Si-Fe alloy processed to produce (110)[001] and (100)[001] texture by secondary growth. The cube-on-edge material was 0.59 mm thick. Suitably large (110)[001] crystals 25 mm wide were selected and their orientations were determined using an optical goniometer. Etch pits for texture determination were formed by a ferric sulfate solution. The other crystals used in the study with (100)[001], (100)[011], and (111)[112] orientations were obtained from sheet which contained large grains developed from secondary recrystallization by a surface-energy driving force.13 Most crystals had a (100) plane very nearly parallel to the sheet surface and the rolling direction could be selected readily. The same sheet also contained a few crystals with (111) planes parallel to the sheet surface, these also being a result of growth by surface energy. The crystals selected from the sheet were about 25 mm wide and 0.25 to 0.28 mm thick. As shown in Table 11, the crystals already contained about 0.070 to 0.10 pct Mn. Inclusions of MnS were incorporated into crystal 36 in the following manner. The crystals were first sulfurized by holding them Table I. Initial Orientations of Crystals Crystal No. Initial Orientation Thickness, mm Special Treatment 34 (I10) [00l]* 0.59 None 36s (110) [001] 0.59 Sulfide precipitates added 30,40 (111)[Ti21 0.28 None 43s (III) [Ti21 0.28 Sulfide precipitates added 37 (100) [Oll] 0.30 None 37C (100) [01I] 0.27 Carbon added 41 (100) (01I] 0.25 None 41C (100) [OI11 025 Carbide precipitates added 42 (100) [OOl] 0.25 None 42C (100) [001] 0.25 Carbide precipitates added *Tilted 4 deg to r~ght about R.D. Table II. Compositions of Crystals Special Treatments Base Analysis ~ ______________________£________________Crys- Crystals Pct Si Pct C Pct Mn Pct S Pct N Pct Al tal Pct C Pct S 34.36 2.93 • 0.099 <0.005 - 0.0014 36S 0.011 30.37 to 42 2.78 0.0057 0.070 0.001 0.0008 0.0011 43S 0.022 37C 0.029 -41C 0.028 -42C 0.026 *Estimate 0.004 pct. Oxygen estimated <0.003 pct on all samples

Jan 1, 1970

By Jaakko Kajamaa

Neutron diffraction was applied to determine sheet textures by the transmission method. Cold-rolled and recrystallized copper sheets were investigated. The amount of cube texture was determined for three compositions, in which the phosphorus content was, respectively, 0, 0.005, and 0.03 wt pct. The heat treatment was in every case 8 sec at 650°C. In the two latter cases the cube texture was prevented. In addition a comparison with the X-ray diffraction transmission method was made with the 96 pct cold-rolled copper sheet. Outer parts of both (111) pole figures can be considered to be rather identical. This is seen from the fact that the intensity ratio ITD/120" was 0.45 for neutron diffraction and 0.40 for X-ray diffraction. Differences between the methods were discussed in detail. Features peculiar to neutron and X-ray diffraction in texture studies were listed and compared. In this work neutron diffraction was applied to determine sheet textures. Specifically, it was desired to ascertain whether this method can be used to reveal differences when compared to other methods. In addition, the amount of the cube texture in copper sheets was determined as a function of phosphorus content. Previous applications of neutron diffraction to texture problems include the following: nickel wires,&apos; wire of some bcc metals,&apos; and uranium bars.3 In the neutron diffraction technique the greatest difference is in the sample—its method of production and its volume. A sample needs no treatment and its volume is roughly 105 times larger than the volume of an X-ray diffraction sample. The cold-rolled sheet was investigated both by neutron diffraction and by X-ray diffraction, because it is expected that, due to large number of defects, possible differences in the results of the two methods would be revealed. It is a well-known fact that X-ray lines show broadening when cold-worked. Analysis has shown that this is based chiefly on small crystalline size, micro-stresses, and/or faults.4&apos;5 Neutrons are sensitive to the above-mentioned disturbing factors as well, but circumstances in diffraction are different from the X-ray case. Because the sample represents a larger volume, the result is an average over that volume. In addition, it can be assumed that the sample has preserved its original structure, because it needs no special preparation. The particular limitation of neutrons is the relatively low neutron intensity available from nuclear reactors. This decreases the resolution as compared to the X-ray diffraction methods. Furthermore, absorption mainly reduces diffracted X-ray intensity, while multiple scattering effects, i.e., secondary extinction, disturb neutron diffraction. SO neutrons and X-rays behave in a different way when interacting with matter. As in other structural investigations, one can utilize this difference in texture studies as well. One cold-rolled and three recrystallization textures in copper sheets were investigated by neutron diffraction. The samples were produced at the Outokumpu copper factory to the specifications shown in Table I. The paper is divided into five parts. The first deals with the theory of the measurement. In the second, experimental procedures are described. Results are presented in the third part. Both cold-rolled and re-crystallized samples are studied. Discussion is in the fourth part, and finally in the fifth part some conclusions are drawn. 1) THEORETICAL CONSIDERATIONS Properties peculiar to neutron diffraction are the following: a) the scattering length varies greatly between one element and another; b) many of the elements do not absorb neutrons appreciably. In this connection it is of primary interest to know the interaction of neutrons with lattice imperfections. As with X-rays this problem leads to diffraction analysis of deformed and recrystallized metals. From the physical point of view the main difference is that neutrons are scattered by nuclei (magnetic scattering is not considered here), whereas X-rays are scattered by electrons. The features peculiar to neutron and X-ray diffraction methods in texture studies are listed in Table 11. Pole figures are an important tool in performing structural analysis of deformed or recrystallized metal. Present texture research technology requires pole figures which are as precise as possible. The choice between these two methods depends on the technical information which is required. The X-ray diffraction transmission technique may give results which are not necessarily representative of the average physical state of the sample. Although foil samples normally contain enough crystallites for diffraction, they may not necessarily represent the whole structure. An example of this problem is the frequently observed difference between the "surface" and the "inside" texture of a sample. The production of foil samples may disturb the original structure of the parent material. The selection and orientation of the foil from the sample is quite arbitrary. Normally, a highly deformed piece of metal has several texture components. Different components are deformed in a slightly different manner. This is a re-

Jan 1, 1969

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of-the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication.1-5 In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators. of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating and distillation in-the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char.6 Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking. qualities by inspection of chemical analyses of coals.7 A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: Coking index =[ a+b+c+d 5] a equals 22/oxygen content on ash and moisture- free basis, . b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/1.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above 1.1 indicate good coking tendencies. Although generally usable, this formula is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct.8,9 Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1952

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young&apos;s modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young&apos;s modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman&apos; noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig&apos; observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity&apos; or the paramagnetic susceptibility.&apos; Likewise, no one has noted a change in crystal symmetry. In the present investigation Young&apos;s modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,&apos; and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.&apos; The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder&apos; the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young&apos;s Modulus: For measurement of Young&apos;s modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young&apos;s modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young&apos;s modulus at 25°C, Fig. la, is 28.2~10" dynes per cm&apos; (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;&apos; the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."&apos; In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.&apos; A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above&apos; 1.1 indicate good coking tendencies. Although generally usable, this formula &apos;is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

By M. L. Leonardi

THE Searles Lake orebody is located in the north- west corner of San Bernardlno County. It is a dry lake bed with an exposed salt surface covering an area of 12 square miles. Recoverable mineral values are contained in the mother liquor below the surface of the lake. Stratification in the lake bed has separated the brine into two bodies which dlffer in composition. Although liquor is processed from both bodies, this paper will discuss only the upper structure brine. Fig. 1 illustrates a typical cross-section of the two commercial orebodies. The orebody is composed of a porous salt deposit 70 to 90 ft deep. The upper structure is separated from the lower orebody by a 12 to 16-ft thick impervious mud seam, as shown in Fig. 1. These salt structures are composed of 55 pct solid-phase salts and 45 pct voids which are filled with the original mother liquor. The brine wells are drilled to the separating mud seam and cased to wlthin 10 ft of the bottom. This is done to draw the brine horizontally from the bottom of the structure. It is pumped with multistage centrifugal pumps Into the plant at the rate of 3 milllon gal per day. The first process that was successful was developed by Charles P. Grimwood for the recovery of potash. The first evaporator unit was built in 1916. In the early twenties, Dr. Morse worked out a process for the recovery of borax. This made the cycle more efficient, as the end liquor could be sent back to the evaporators rather than being sewered. In 1926 the American Potash & Chemical Corp. was formed as a new company, and the entire plant was remodeled. The plant at that time produced only potash, borax, and boric acid. Since then the American Potash & Chemical Corp. has added processes for the production of USP boric acid, refined potash, sulphate of potash, soda ash, salt cake, lithium concentrates, Pyrobor (Na2B4O7) bromine, phosphoric acid, and lithium carbonate. The main plant cycle may be depicted as a closed cycle, see Fig. 2. The raw material, brine, enters the cycle to be mixed with the end liquor, known as ML2, from the pentahydrate borax crystallizers. The mixture of these two forms evaporator feed. Evaporator feed is pumped to the evaporators where it is concentrated, with respect to potash and borax. In the same operation water vapor, sodium chloride, salt trap salt, and clarifier salt are removed from the cycle, see Fig. 3 for potash plant product. The evaporators produce a concentrated liquor which contains approximately 19.5 pct KCI. This liquor is diluted as it enters the potash plant to keep all salts, except potash (KCI, 97.0 pct) in solution. Here the moist potash leaves the cycle at 100°F. The end liquor, known as ML1, is pumped to the borax pentahydrate crystallizers, where crude borax pentahydrate is crystallized and removed as solid phase. The ML2 is sent back to pan feed to be reconcen-trated, see page 207. Note that the only water to leave the cycle is in the form of vapor and moisture in the solid phase products crystallized. Thus there is a constantly cycling volume of liquor to which brine is added. Since the volume of liquor cycled does not increase, the brine is, in effect, evaporated to dryness. This would be true if there were no liquor losses. But, as in all processes, there are always unavoidable and accidental losses which reduce the volume of cycling liquors. The losses must be made up with brine. The concentration process is the beginning and the end of the cycling liquors. In this process there are three evaporator units of the triple effect counter-current type, that is, there are three pans in each unit and the heat flows in one direction while the liquor flows the other way through the evaporator pans, see Fig. 4. During the evaporation process a great deal of sodium chloride, burkeite, some sodium carbonate monohydrate, and a little lithium-sodium phosphate are crystallized. The volume of these salts is so great that they must be removed as they are formed or the process would come to a standstill. Brine and recycled mother liquor No. 2 enter the third effect evaporator pan from the evaporator feed storage tanks, see Fig. 5. A steady flow of liquor is removed from the bottom of the No. 3 pan and is pumped through the No. 3 cone of the salt trap, a clear liquor being returned to the NO. 3 pan. A portion of this clear liquor is pumped to the second effect pan. This process is repeated in each pan. The liquor from the No. 2 pan is pumped through the No. 2 salt trap cone and returned to the No. 2 pan.

Jan 1, 1955

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

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

Jan 1, 1955

By B. S. Crocker

Pebble grinding was used at Lake Shore Mines in 1949. A full description of experimental evidence and test plant results was published in 1952 1 and further operating details in 1954 2.&apos; In more recent years the term autogenous grinding has been coined and is now frequently seen in the technical literature. Autogenous crushing and/or grinding covers any grinding mill in which the larger pieces of ore are made to grind the fine pieces; the crushing and grinding may be either dry or wet. This discussion deals only with wet autogenous grinding, and only in the fine grinding part of the circuit, i.e., from 6 mesh to 92 pct —325 mesh. The term pebble milling could apply to fine autogenous grinding in which the pebbles are made from the ore itself, or it could also refer to grinding with pebbles, such as flint pebbles, from a source outside the mine. The first mill to use screened ore to grind the ore (1949) was Lake Shore Mines, Kirkland Lake, Ont. Pebbles were screened from the jaw crusher discharge and used in 5x16-ft tube mills which had been converted to 6 ft 8 in. by 16-ft grate discharge pebble mills. The same general practice was adopted the following year by the Wright-Har-greaves Mine in Kirkland Lake. Shortly after that the Neptune Mines in Nicaragua started correspondence with the writer concerning the possibility of using screened ore for grinding in their plant. They first ran some plant-scale tests which confirmed the Lake Shore findings, with the ultimate result that their plant was successfully converted in 1956 to an autogenous grinding plant. In 1957-1958 the writer was successful in converting the grinding plant of Renabie Mines in northern Ontario to autogenous grinding. In all these plants the existing grinding equipment was converted, usually by expanding the diameter of the shell to make the change from steel grinding to ore pebble grinding mills. In all the above plants primary grinding was done in either small rod mills or ball mills. These mills first reduced the pebble mill feed to about 6 mesh. The final grinding in the pebble mills varied from 75 pct —200 mesh to 92 pct —325 mesh. At Lake Shore three stages of pebble milling were used, with a different size pebble in each stage. In other parts of the world interest was being shown in this form of grinding, and in March 1952 the writer had some correspondence with the mill staff at Outokumpu in Finland, with regard to the pebble system used at Lake Shore. At Stockholm in 1957 the account of the crushing and grinding system at Outokumpu was presented in a paper by H. Tanner and T. Heikkinen.V his is the only ore grinding plant that does not use grate discharges on its pebble mills; trunnion discharges equipped with heavy reverse spirals retain the pebble load. The first new mill designed to use screened ore as a grinding medium was the Bicroft mill at Bancroft, Ont., which began operation in the fall of 1956. In 1957 this plant was followed by similar installations at Faraday Mines, also in the Bancroft area, and the North Rankin Nickel Mines in the North West Territories. In 1958 the Dyno Mill at Bancroft was converted, using the same type of grinding. Since all these plants, designed by Kilborn Engineering (1954) Ltd., were originally planned as pebble grinding mills, they were able to take full advantage of the latest design and technique. They are neat in appearance and very efficient and easy to operate. Effect of Ore Hardness: It is often commented that this type of autogenous grinding applies only to hard siliceous ores. Experience has shown that this is not so. In the past ten years the author has had an opportunity to test more than a dozen ores, several of which were quite soft. One of these was shale. The softer ores actually make better looking pebbles than the hard ores. These soft ores produced no particles in the intermediate size range which could not be ground by the largest pebbles in the mill charge. Slabby ores, such as shales, make a suitable pebble for the —6 mesh grinding. It is not generally recognized that for fine grinding a spherical medium is not essential or more efficient. Another frequent objection to pebble grinding is the belief held by some operators that there is too much variation in the hardness of their particular ore to make it acceptable as a source of pebble media. Experience has also shown that this is not a serious problem at all. The variation in pebble load due to changes in the ore hardness is nothing like as great as most people would expect, and the method used for feeding the ore and controlling the the load in the mills is more than sufficient to take care of daily variations in ore hardness. This point

Jan 1, 1960

By P. E. Doherty, B. Chalmers

Subboundaries may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits do not form in the vicinity of high- or low-angle boundaries. They are attributed to the condensation of vacancies from a super saturation produced during coolirzg. Using the vacancy pit and Schulz X-ray techniques for observing low-angle boundaries, a study was made of the transition from the nearly perfect seed to the striated structuke characterist-ic of aluminum crystals grown from the melt. It was found that the individual striation boundaries develop by the coalescence of very small-angle boundaries, as well as by the addition of individual dislocations. Several mechanisms for the formation of striations are discussed. Evidence was found suggesting that a super-saturation of vacancies exists near a growing interface, and it is proposed that the resulting climb of existing dislocalions produces "half&apos;-loops" at the interface, which combine to form the low-angle striation boundaries. LINEAGE, or "striation" boundaries, have been studied in detail by Teghtsoonian and Chalmers 1,2 in crystals of tin grown from the melt, and by Atwater and Chalmers3 in lead. They found that single crystals grown from the melt consist of regions which are separated by subboundaries that lie roughly parallel to the growth direction. A difference in orientation of 0.5 to 3 deg exists between the striated regions; the misorientation is such that the lattice of one region could be brought into coincidence with the lattice of its neighbor by a rotation about an axis approximately parallel to the direction of growth of the crystal. They observed an incubation distance for the formation of striations which increased with decreasing growth rate. They also found that in any crystal, the sum of all rotations of the lattice in one sense, in going from one striation to the next, is very nearly equal to the sum of all the rotations in the opposite sense. A striation boundary, which is a low-angle grain boundary, can be described as an array of dislocations. If it is assumed that suitable dislocations are introduced into the crystal during solidification, the formation of striation boundaries can be explained as a result of the migration of the disloca- tions into arrays. The formation of arrays is energetically favorable since the energy of an assembly of dislocations can be reduced by the interaction of the stress fields when a suitable array is formed. This investigation presents and interprets new information concerning the nature and origin of striation boundaries in aluminum. EXPERIMENTAL TECHNIQUE Single crystals of high-purity aluminum (Alcoa 99.992 pct) were prepared by horizontal growth from the melt.&apos;&apos; The specimens were subsequently electropolished in a solution of 5 parts methanol to 1 part perchloric acid kept between -10° and 0°C in a bath of dry ice and alcohol. The current density was approximately 6 amps per sq in. Doherty and Davis9 have shown that in aluminum sub-boundaries with misorientations of not less than several seconds of arc may be revealed by the vacancy pit technique. During cooling from elevated temperatures pits form on electropolished surfaces of aluminum crystals as a result of the condensation of vacancies.11 Pits do not form in the vicinity of small- or large-angle grain boundaries, presumably because such boundaries act as sinks for vacancies. Boundaries of misorientations down to 3 sec of arc are revealed as pit-free regions, see Fig. 1. The Schulz X-ray technique12 was used to determine the angular misorientations of subboundaries. In this method, white radiation from a micro-focus X-ray tube is used to produce an image of a fairly large area of a single crystal surface. Subboundaries cause splitting in the diffracted image, see Fig. 2. Misorientations down to about 15 sec of arc may be observed with this technique. OBSERVATIONS AND DISCUSSION Figure 1 shows a striated aluminum crystal grown at 10 cm per hr etched by the vacancy pit technique. An incubation distance of about 1 cm is observed before the initiation of striation boundaries. Fig. 2 is a Schulz X-ray photograph of a striated crystal similar to that shown in Fig. 1. A large area of the crystal was studied by means of a series of photographs. Fig. 2, which is a reflection from the (100) plane, included about the first 4 cm of crystal to freeze. There is an incubation distance of about 1 cm, and a distance of about 2 cm over which the angle of misorientation builds up to its final value of approximately one degree. Some twist component can be seen in Fig. 2 at the right side of the photograph. From Fig. 2 it can be seen that the sum of all rotations of the lattice in one

Jan 1, 1962

By Joseph Fry, Ralph H. Espach

In the spring of 1943, when it was evident that the Tensleep bandstone in the Elk Basin Field, Wyoming and Montana, held a large reserve of petroleum, Bureau of Mines engineers obtained samples of oil from the bottom of nine wells and analyzed them for such physical characteristics as the volumes. of gas in solution. saturation pressures or bubble points, shrinkage in volume caused by the release of gas from solution, expansion of the oil with decrease in pressure, and other related properties. The composition of the gas in solution in the oil was studied. The pressures and temperatures existing in the reservoir and the productivity characteristics of the oil wells were determined. The data obtained indicate that the oil in the Tensleep Reservoir of the Elk Basin Field has unusually varying physiral characteristics, such as a saturation pressure of 1,250 psia and 490 cu ft of gas in solultion in a barrel of oil at the crest of the structure and a saturation pressure of 530 psia and 134 cu ft of gas in solution in a barrel of oil low on the flanks. The hydrogen sulfide content of the gas in solution in the oil varies from 18 per cent for oil on the crest to 5 per cent for oil low on the flanks of the structure. Of even greater significance is the fact that these and other variable characteristics of the reservoir oil are related to the position of the oil in the structure. Many geologists and petroleum engineers have considered that all the oil in a petroleum reservoir has rather uniform physical characteristics and that equilibrium conditions prevailed in all underground accumulations of oil and gas; that such is not always so is borne out by the results of the study by the writers. INTRODUCTION The Rocky Mountain region is one in which may be found striking examples of the unusual in oil and gas accumulations, as is evident from the following: The high helium content (7.6 per cent) of the gas in the Ouray-Leadville limestone sequence in the Rattlesnake Field, New Mexico, and gases of similar helium content in other fields; 50" to 55&apos; API gravity distillate in solution in carbon dioxide gas and recoverable through retrograde condensation, in the North McCallum Field, Colorado; the occurrence of gas, oil, or both in closely related structures contrary to the usual concepts of gravimetric segregation: the accumulation of gas and/or oil in structures closely related to other structures that apparently are more favorable but do not contain oil or gas accumulations; the high hydrogen sulfide content (as high as 42 per cent) of the gas associated with oil in some fields in the Big Horn Basin, Wyoming; and the wide range of fluid chararteristics found in the Elk Basin reservoir. Elk Basin, an interesting old oil field that has been producing oil from the Frontier formation since 1915, is situated in a highly eroded basin resulting from the erosion of the crest of an anticline and some of the underlying softer shales. The field came back into national prominence during 1943 when it became known that it was the largest single reserve of new oil discovered in the United States that year. The Tensleep sandstone was found to contain oil in November. 1942, when a well drilled to a depth of 4,538 ft (44 ft into the Tensleep sandstone) flowed oil at the rate of 2,500 B/D. By the end of 1949, 137 oil-producing wells and five dry holes had been drilled, and approximately 32 million bbl of oil had been produced. Approximately 6,000 acres may be considered productive of oil in the Tensleep Reservoir, and estimates of the oil that will be produced average 200 million bbl. The Tensleep Reservoir has further interest because it ha-greater closure than any oil field in the Rocky Mountain region; the closure of the Elk Basin anticline is variously estimated at 5.000 to 10,000 ft. of which the top 2.00 ft of the structure contained oil. SUBSURFACE OIL SAMPLING Fig. 1 is a structural map of the Elk Basin Tensleep Reservoir, on which the nine wells used in this study and the numbers correvponding to the well designations hereafter referred to are shown. Wells 1. 2, 3, 4, and 8 were tested and sampled during October and November. 1943. and Wells 5, 6. 7, and 9 during June and July, 1944. An electromagnetic type sampler developed by the Bureau of Mines and described by Grandone and Cook&apos; was used in obtaining the subsurface oil samples. As the wells were tubed nearly to bottom, the sampler was run as far as possible in the tubing hut never below the top perforations. The following procedure was used in testing and sampling the wells: A well was shut in for at least three days, after

Jan 1, 1951

By Che-Yu Li, J. L. Gregg, W. F. Brehm

Oriented, oxygen-doped niobium bicrystals were tested in liquid lithium. The grain boundaries were attacked preferentially. The depth of the penetrated zone varies as (time)2. The penetration was aniso-tropic, had a high activation energy, and increased with the increased oxygen doping level. A possible model was proposed to account for the experimental observations. 1 HE grain boundary penetration of a metallic system by liquid metal has been studied by several investigators. Their results are summarized by Bishop.&apos; Most of these works show that the penetration by liquid metal corresponds to the phenomenon of liquid metal wetting. In the case of a grain boundary, wetting will occur when twice the solid-liquid interfacial tension is smaller than the grain boundary tension resulting in the replacement of the grain boundary by two new solid-liquid interfaces. Other possibilities exist; for example, the atoms of the liquid metal may diffuse into the grain boundary region due to chemical potential gradient. The gradient can be produced by impurity segregation or simply be due to the increase in solubility in the grain boundary region. The penetrated grain boundary in these cases may remain solid at the test temperature. The Nb-Li system has been of considerable interest because of its possible technological applications. For fundamental interest it provides a possibility of studying the grain boundary penetration process which is not controlled by the wetting mechanism. The pure niobium is not attacked by the liquid lithium, but if niobium containing more than 300 to 500 ppm oxygen by weight is exposed to liquid lithium, corrosion occurs at the solid-liquid interface and preferentially at grain boundaries. Previous investigators2-&apos; have proposed that this preferential corrosion at grain boundaries is caused by oxygen segregation there, with subsequent inward diffusion of lithium to form a Li-Nb-0 compound. These investigators also found that the corrosion could be retarded by adding 1 pct Zr to the niobium to precipitate the oxygen as ZrO2 upon proper heat treatment. However, there are no quantitative data on the kinetics of the grain boundary penetration process to test the validity of the proposed corrosion mechanism. In this work an investigation of this penetration process in oriented bicrystals was made as a function of the oxygen doping level in the bulk niobium and the grain boundary orientation. A possible model for the penetration process based on the experimental results was proposed. EXPERIMENTS Oriented niobium bicrystals were grown by arc-zone melting oriented single-crystal seeds.7 These bicrystals contained simple tilt boundary. The [001] directions in the two grains were tilted about a common [110]. The bicrystals were 31/2 in. long and 5 by 4 in. in cross section with the straight, symmetric, planar grain boundary longitudinally bisecting the crystal rod. The bicrystals were doped with oxygen by anodically depositing a layer of Nb2O on the surface in a 70 pct HNO solution at 100 v, using a stainless-steel cathode. The specimens were homogenized by annealing in evacuated quartz tubes at 127 5°C. Oxygen content of the niobium was measured from microhardness values, after DiStefano and Litmman.&apos; Supplementary checks were made with vacuum-fusion analysis.7 Individual test specimens cut from the doped bi-crystal rods, about by by % in. in size, were tested inside double jacket sealed capsules. The inner jacket was niobium, the outer was stainless steel. The niobium inner jacket eliminated the problem of dissimilar-metal mass transfer.&apos; The lithium (99.8 pct pure, obtained from Lithium Corp. of America) was handled only in a purified argon atmosphere in a Blickman stainless-steel glove box. After introduction of lithium, the capsules were sealed by welding. Further detailed experimental procedures are given in Ref. 7. The capsules were heat-treated in vertical Marshall resistance furnaces. Temperatures were controlled to When heating above 1100°C, it was necessary to seal the furnace work tube and flow argon through to prevent failure of the stainless-steel outer jacket of the capsule. Tests were made on 6" 2", 16" 2, and 33" i2" bicrystals at oxygen levels up to 2600 ppm by weight in the 6&apos; and 16" crystals and with 1300 ppm oxygen in the 33&apos; crystals. The oxygen levels were controlled to 100 ppm. Most of the quantitative data were obtained from 16" bicrystals between 800" and 1050°C. The capsules were quenched into water after the test and cut open with a water-cooled abrasive wheel. The capsules were then submerged in water, which dissolved the lithium and freed the specimen. Measurement of the depth of the penetrated zone in the grain boundary was done either on metallographically prepared surfaces or directly on the grain boundary plane after the specimen was fractured in tension in the grain boundary plane. The depth of penetration measured by both methods agreed well. Further details describing these techniques have been reported elsewhere.&apos;p7

Jan 1, 1969

By Joseph Fry, Ralph H. Espach

In the spring of 1943, when it was evident that the Tensleep bandstone in the Elk Basin Field, Wyoming and Montana, held a large reserve of petroleum, Bureau of Mines engineers obtained samples of oil from the bottom of nine wells and analyzed them for such physical characteristics as the volumes. of gas in solution. saturation pressures or bubble points, shrinkage in volume caused by the release of gas from solution, expansion of the oil with decrease in pressure, and other related properties. The composition of the gas in solution in the oil was studied. The pressures and temperatures existing in the reservoir and the productivity characteristics of the oil wells were determined. The data obtained indicate that the oil in the Tensleep Reservoir of the Elk Basin Field has unusually varying physiral characteristics, such as a saturation pressure of 1,250 psia and 490 cu ft of gas in solultion in a barrel of oil at the crest of the structure and a saturation pressure of 530 psia and 134 cu ft of gas in solution in a barrel of oil low on the flanks. The hydrogen sulfide content of the gas in solution in the oil varies from 18 per cent for oil on the crest to 5 per cent for oil low on the flanks of the structure. Of even greater significance is the fact that these and other variable characteristics of the reservoir oil are related to the position of the oil in the structure. Many geologists and petroleum engineers have considered that all the oil in a petroleum reservoir has rather uniform physical characteristics and that equilibrium conditions prevailed in all underground accumulations of oil and gas; that such is not always so is borne out by the results of the study by the writers. INTRODUCTION The Rocky Mountain region is one in which may be found striking examples of the unusual in oil and gas accumulations, as is evident from the following: The high helium content (7.6 per cent) of the gas in the Ouray-Leadville limestone sequence in the Rattlesnake Field, New Mexico, and gases of similar helium content in other fields; 50" to 55&apos; API gravity distillate in solution in carbon dioxide gas and recoverable through retrograde condensation, in the North McCallum Field, Colorado; the occurrence of gas, oil, or both in closely related structures contrary to the usual concepts of gravimetric segregation: the accumulation of gas and/or oil in structures closely related to other structures that apparently are more favorable but do not contain oil or gas accumulations; the high hydrogen sulfide content (as high as 42 per cent) of the gas associated with oil in some fields in the Big Horn Basin, Wyoming; and the wide range of fluid chararteristics found in the Elk Basin reservoir. Elk Basin, an interesting old oil field that has been producing oil from the Frontier formation since 1915, is situated in a highly eroded basin resulting from the erosion of the crest of an anticline and some of the underlying softer shales. The field came back into national prominence during 1943 when it became known that it was the largest single reserve of new oil discovered in the United States that year. The Tensleep sandstone was found to contain oil in November. 1942, when a well drilled to a depth of 4,538 ft (44 ft into the Tensleep sandstone) flowed oil at the rate of 2,500 B/D. By the end of 1949, 137 oil-producing wells and five dry holes had been drilled, and approximately 32 million bbl of oil had been produced. Approximately 6,000 acres may be considered productive of oil in the Tensleep Reservoir, and estimates of the oil that will be produced average 200 million bbl. The Tensleep Reservoir has further interest because it ha-greater closure than any oil field in the Rocky Mountain region; the closure of the Elk Basin anticline is variously estimated at 5.000 to 10,000 ft. of which the top 2.00 ft of the structure contained oil. SUBSURFACE OIL SAMPLING Fig. 1 is a structural map of the Elk Basin Tensleep Reservoir, on which the nine wells used in this study and the numbers correvponding to the well designations hereafter referred to are shown. Wells 1. 2, 3, 4, and 8 were tested and sampled during October and November. 1943. and Wells 5, 6. 7, and 9 during June and July, 1944. An electromagnetic type sampler developed by the Bureau of Mines and described by Grandone and Cook&apos; was used in obtaining the subsurface oil samples. As the wells were tubed nearly to bottom, the sampler was run as far as possible in the tubing hut never below the top perforations. The following procedure was used in testing and sampling the wells: A well was shut in for at least three days, after

Jan 1, 1951

By J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959

By Emerson F. Heald

A systematic study was made of new and old data on chemical activities in Fe-Pt alloys at elevated ternperatuves. Experimental results may be expressed in terms of the excess free energy using Least-squares analysis of the data gave the following values for the constants: for the temperature range 1130° to 1350°C, and tentatively to 155O°C, B = -3.326564 and C = 0.221051; for the temperature range 650" to 850°C, B = -2.555690, C = 1.762735, and D =0.097196. In the study of iron-containing silicate systems, it is sometimes desirable to have a direct experimental measure of the activity of iron in the system. The well-known solubility of iron in platinum, often a headache in experimental work on iron compounds under reducing conditions, can be used to advantage in this respect. If the activity of iron in an Fe-Pt alloy in equilibrium with the silicate is known as a function of the composition of the alloy, chemical analysis of the alloy will give a knowledge of the activity of iron in all of the phases in the system. The present study was undertaken in order to elucidate the characteristics of Fe-Pt alloys as iron activity indicators. This work is intended to tie together some previous work, which may be summarized as follows. Larson and Chipman1 determined the activity of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with calcium oxide-iron oxide-silica melts of known iron activity. Compositions of the resulting alloys were determined by chemical analysis. A similar study was carried out by Taylor and ~uan,&apos; who worked at 1300°C. They brought the Fe-Pt alloys into equilibrium with iron oxide under conditions of known partial pressure of oxygen, and thus, from the work of Darken and ~urr~,~ conditions of known iron activity. Compositions were determined indirectly, by following the change in weight of the sample. Sundaresen et el* used the electromotive force of cells in which the alloy formed one electrode in order to measure the activity of iron in the alloy at 650" and 850°C. These temperatures were chosen to be above and below the first-order phase transition which takes place upon the ordering of Fe3Pt and the second-order transition which occurs upon the ordering of FePt3. EXPERIMENTAL 1) High Temperatures. The starting materials used were thin platinum foil, about 0.002 mm thick, and Fisher Certified reagent ferric oxide, Fez03, which had been heated for 24 hr at 1000°C. An intimate mixture of 80-mesh Fez03 and platinum platelets was placed in a thin platinum foil envelope. The latter was suspended from thin platinum wires in the hot zone of a vertical-tube, platinum-wound furnace of the type described by Muan and ~sborn.~ A capillary gas mixer similar to that used by Darken and Gurry3 was used to prepare a precisely known mixture of carbon dioxide and hydrogen, which was allowed to flow upward through the furnace tube. The partial pressure of oxygen in contact with the sample was thereby fixed at a value which was calculated from the charts prepared by porter? Temperatures were measured with a Pt-10 pct Rh-in-platinum thermocouple, which was calibrated using the melting points of gold (1062 .@C) and diopside, CaMgSizOB (1391.5"C). Temperature control was maintained to within i3"C with a Geophysical Laboratory proportional controller, using the furnace resistance as the sensing element. Samples were quenched by passing a small current through the platinum suspension wires, allowing the sample to drop into a bath of dibutyl phthalate at the bottom of the furnace tube. Prior to chemical analysis the samples were washed with acetone and dried. 2) Chemical Analysis. It proved possible, in almost all cases, to separate the Pt-Fe platelets physically from particles of iron oxide. The platelets were dissolved in a small volume of aqua regia, evaporated to dryness, and redissolved to 0.1 M HC1. In order to determine iron in the platinum alloy potentiometrically, it is necessary first to remove the platinum. A 10-cm column of Amberlite IR-120 cation exchange resin in the hydrogen form provided separation quickly and quantitatively: The mixture of iron and platinum in 0.1 M HC1 was added to the top of the column, and washed with about 100 ml of 0.1 M HC1. Under these conditions, the iron, principally in the form of cations such as FeC1" and FeCl;, is held quantitatively in the uppermost centimeter of the column. The platinum, in the form of anions such as PtC&- , is washed through without being adsorbed. After a qualitative test with stannous chloride indicated all of the platinum was removed, the iron was

Jan 1, 1968

By J. E. Ryan

TRONA, Calif., is a miniature urban community of some 3500 people, located on the northwest shore of dry Searles Lake in the extreme northwest corner of San Bernardino County, approximately 186 miles north and east of Los Angeles. Since it is situated on the Mojave Desert, a typically desert climate prevails with wide variations in temperature between day and night, extreme daytime summer heat, and cool to cold winters. Rainfall averages somewhat less than 4 in. per year, and dust storms are common. The rate of evaporation, .however, is great, amounting to 6 to 9 ft of water per year. The extremely low humidity makes the summer heat of 110°F tolerable with only a mild, temporary discomfort. Nature of Deposit During the periods when Searles Basin was flooded, the waters that passed through Indian Wells Valley spread out to form a broad, shallow lake providing, in effect, a settling basin for suspended sediment. The drainage into the deeper and more isolated Searles Basin thus was clarified to a great degree before concentration began. Today, the elevation of the dry surface of Searles Lake is 1618 ft, and the salt deposit measures 5x7 miles. At the eastern and northeastern margins of the main playa zone and just at the foot of the alluvial slope of sand and coarser wash from the Slate Range mountains, a rim of crusted salts rises a few feet above the level of the flat. The deposit is a saline efflorescence composed of salts that were presumably brought up with rising ground waters to be deposited at the surface by solar evaporation. This deposit consists chiefly of trona, and it is after this Trona Reef that the town Trona was named. Strip mining operations have been conducted in the past at infrequent intervals for the recovery of crude trona salts. The main focal point of interest in Searles Lake from a commercial standpoint is the main salt body located almost centrally in the basin. The exposed portion of this porous saline deposit covers approximately 12 sq miles and averages 71 ft deep. Its interstitial voids, which constitute 50 pct of the total volume, are permeated with a brine, which is in equilibrium with the soluble salt deposits. The brine is the raw material for the operations of the American Potash and Chemical Corp. plant at Trona, shown in Fig. 1. The soluble salt deposits are of interest for their potential values in future technologic development. The brine, which is stratified according to slight differences in density, stands usually within 6 in. of the surface of this exposed, firm, salt body. The surface is usually dry and will support the weight of heavy mobile units and drilling equipment. Occasionally, however, surface waters from the higher watersheds encroach upon the main salt body during infrequent periods of precipitation on the surrounding mountains. This water dissolves surface salt, becomes a dilute brine, and has been observed to stand as high as 18 in. above the salt surface when undisturbed. Windstorms will shift the water back and forth across the lake surface. The exposed salt body is surrounded by additional submerged areas of commercial soluble salt deposits covering some 20 sq miles, hidden from view by marginal playa mud. These vary in depth up to as much as 30 ft. Thus, the outline of exposed and submerged salt deposits of commercial value is estimated to cover a total area of 32 sq miles, which is roughly circular but slightly elongated from northwest to southeast. It has been estimated that each square mile contains about 100 million tons% f alkali salts. The results of drill borings in the past 15 years have brought to light the interesting fact that the main salt body lies superimposed on an impervious mud deposit from 10 to 15 ft thick containing relatively little soluble salt. Under this deposit lies a second soluble salt body 35 ft deep. The lower salt body is interspersed with numerous insoluble mud lenses and its composition is considerably different from that of the primary, or main salt deposit. Recent drill borings have not penetrated beyond 300 ft. They have, however, revealed that underlying the lower salt body, the mud sediments carry deposited minerals of trona, nahcolite, mirabilite and much less soluble carbonates or sulphates of calcium and/ or magnesium. This structure is shown in Fig. 2. Current Lake Survey Program Several hundred holes have been drilled in the deposit. However, to carry out a thorough and carefully correlated study of the composition of the soluble salts and other minerals in the dry lake basin, a drilling program was inaugurated recently and is now nearing completion. In this survey, pattern drill holes are sunk at regular lh-mile intervals to a depth of approximately 150 ft. Drilling equipment consists of a No. 51 C. P.

Jan 1, 1952

By D. F. Atkins, B. A. Rogers

The constitutional diagram presented herein is relatively simple. Complete mutual solid solubility exists for an interval below the solidus line, a continuous curve with a flat minimum near 22 pct Cb and 1740°C. Upon cooling, the solid solution breaks up, except at the columbium-rich side, from two causes: zirconium-rich alloys transform under the influence of the ß-a transformation in zirconium; alloys of intermediate composition decompose into two solid solutions below 1000°C. The combined effect is the formation of a eutectoid at a temperature of 610°C and a composition of 17.5 pct Cb. The eutectoid horizontal extends from 6.5 to 87.0 pct Cb. Some age hardening effects have been observed in the zirconium-rich alloys but the positions of the solvus lines remain uncertain. IN recent years, zirconium has been produced in much larger quantities than were available previously. Correspondingly, the incentive for studying its alloy systems has increased, as the number of recent publications on alloy systems testifies. However, only a partial diagram of the Zr-Cb system has been published and relatively few references have been made to alloys of the two metals. Hodge&apos; investigated the Zr-Cb system up to about 25 pct Cb. His data on melting points were not sufficiently numerous to distinguish with certainty between the alternatives of a narrow eutec-tic horizontal and a wide flat minimum in the solidus curve. Although Hodge considered his results on transformations in the solid state to be only tentative, he suggested that the eutectoid in the zirconium-rich alloys lay at about 625 °C and 10 pct Cb and estimated that the solubility of colum-bium in zirconium at 625 °C was near 6 pct. According to Simcoe and Mudge,2 less than 0.5 pct Cb is soluble in zirconium at 800°C. These authors observed an increased strength in both the 0.5 and I pct Cb alloys made with hafnium-containing zirconium. According to Keeler,3 the strength of zirconium is increased by addition of columbium to a content of at least 3 pct. Keeler&apos; also observed a maximum in hardness at about 10 atomic pct Cb and commented on the brittleness of alloys of this composition. Anderson, Hayes, Rober-son, and Kroll5 investigated the tensile properties of Zr-Cb alloys containing 5.1 and 12.9 pct Cb at room temperature and at 343°C. The 12.9 pct alloy had a high tensile strength at room temperature but also a low percentage of elongation. All alloys had high elongation at 343 °C. Littona measured strength and elongation values of annealed alloys containing up to 27.5 pct Cb and found low elongation values for all of the alloys of high columbium content. Some observations on the resistance of Zr-Cb alloys to corrosion in water at high temperature have been published by Lustman, De Paul, Glatter, and Thomas&apos; who found that additions of columbium up to 1 pct had only a minor effect on the corrosion resistance of zirconium. Preparation of the Alloys Raw Material: Zirconium of a relatively good grade was available for making the alloys. It was obtained as scrap pieces that had been left over from an operation that included production by the iodide process, melting under a protecting atmosphere, and fabrication to plates. The individual pieces had hardness values of 24 to 32 Ra and a typical analysis is shown in Table I. The columbium also was scrap trimmed from sheets. It was furnished by the Fansteel Metallurgical Corp. and had a high ductility but its analysis was known only approximately. The metal probably contained about 0.5 pct Ta, perhaps 0.25 pct C, and a few hundredths percent each of iron, silicon, and titanium. Melting: The alloys were melted in a tungsten-electrode copper-crucible arc furnace similar to units that have been described recently in the metallurgical journals.&apos;.&apos; The crucible of this furnace is provided with a cavity in which a getter charge can be melted before the melting of the alloy charges. Hardness measurements on the ingots indicate that the getter charge takes up a considerable fraction of the oxygen and nitrogen from the helium atmosphere of the furnace. The alloys used in the investigation are given with their intended compositions, hardness, and melting points in Table 11. Fabrication: All alloys of the Zr-Cb system appear to be amenable to fabrication. At least, all of the compositions listed in Table II could be reduced to wires in a rotary swaging machine. The starting material was either slabs cut from ingots and ground by hand to rough cylinders or narrow strips trimmed from sheets made by cold rolling slabs. However, not all of the alloys could be fabricated satisfactorily by the same method. From 0 to 4 pct Cb and from 20 to 30 pct Cb or more, the alloys could be swaged cold from ¼ in. cylinders to 0.80 mm wires with only one intermediate annealing, sometimes with none. From 40 to 90 pct Cb, the alloys were difficult to swage either hot or cold but could

Jan 1, 1956

By R. D. Pehlke, P. D. Goodell, R. W. Dunlap

The rate of dissolution of steel bars in molten pig iron has been measured experimentally in the temperature range 2300° to 2650° F. The rate of solution is shown to be a .function of bath composition, temperature, and stirring. A kinetic model based on carbon diffusion in the liquid phase has been derived to fit the experimental results. THE rate of scrap melting has long been an important variable in steelmaking operations. With the advent of the oxygen steelmaking process and the accompanying shorter heat times, the rate of scrap melting has now become one of the rate-limiting factors in steel production. As observed in commercial practice, the solution rate is influenced by the compositions of liquid and solid, the temperature, agitation, and time. However, no definitive work has been done on the Fe-C system, and there is very little information in the literature regarding the relative effects of these variables in steelmaking systems. A number of questions have been raised in regard to scrap utilization in basic oxygen steelmaking operations. Consideration has been given to the optimum size and shape of scrap, and to the use of preheated scrap as a means for decreasing the pig-iron requirement in oxygen blowing. The determination of an optimum scrap practice for a specific installation depends to a large extent upon the economics of the scrap market and also upon the behavior of scrap in the vessel. The present research was undertaken as a preliminary study in evaluating the behavior of steel in a pig-iron bath under various conditions of temperature, composition, and agitation, as might be encountered in oxygen converter operations or in any steelmaking operation where scrap behavior is an important process variable. Related studies have been carried out on non-ferrous systems. The solution rate of solid aluminum in a molten A1-Si alloy has been studied.&apos; Furthermore, the increasing use of liquid metals has created considerable interest in studies related to dissolution of a solid in a liquid, or mass transfer taking place between a solid interface and a liquid metallic phase.2-10 In an effort to clarify the relative importance of factors influencing the dissolution of scrap in Fe-C alloys, this paper presents the results of a study of the rate of dissolution of a low-carbon steel cylinder in a molten Fe-C bath at various bath compositions, temperatures, and conditions of agitation. An attempt has been made to determine the mechanism of solution, and a model has been derived to fit the experimental results. The rate of heat transfer between the molten pig-iron bath and the solid-steel cylinder has also been studied. EXPERIMENTAL PROCEDURE A molten bath of pig iron (nominal composition 4.2 pct C, 0.5 pct Mn, 0.8 pct Si)* was held in a 200- *In view of the fact that the composition of the pig-iron bath was slowly changing with time because of steel dissolution and reaction with the surrounding atmosphere, intermittent samples of the liquid bath were taken throughout each experiment, Table 1. lb induction melting unit. The internal diameter of the furnace was 8-1/2 in. and the bath depth approximately 14 in. Cold-finished 1020 steel cylinders of 1/2-, 3/4-, 1-, 1-1/2-, and 2-in. diameters were cut into 1 -ft lengths for use as test specimens. One end of each bar was machined to fit a hand-driven, mechanical stirring device which rested on top of the furnace. This fixture permitted 7 to 8 in. of the bar to be immersed in the melt. The steel cylinders were cleaned to free the surface of grease and oxide. The rods, at ambient temperature, were immersed into the molten pig-iron bath. The melt temperatures studied in this investigation were 2300°, 2500°, and 2650°F. Different agitation conditions were achieved by operating with a) the power to the furnace, giving induction stirring; b) induction stirring plus mechanical stirring, using hand rotation with a chain and sprocket assembly at approximately 200 rpm; c) mechanical stirring alone with the power off; and d) the power off and no mechanical stirring resulting in minimum agitation, i.e., only that caused by natural convection currents in the bath. The samples were immersed in the melt for prescribed times ranging from 30 sec up to 6 min. Immersion times were measured with a stopwatch and temperature control of the melt was achieved by power adjustment following temperature measurement with an optical pyrometer. The measurements with the calibrated pyrometer were checked out to within less than 10°F with simultaneous thermocouple measurements. Following immersion, the bars were water-quenched and the diameters were measured with a micrometer at several positions on the reduced area, and by volumetric displacement. The dissolution rates calculated from the

Jan 1, 1965

By Jerome J. English, Gordon W. Powell

An experimental investigation and mathematical analysis of the thermal-dilation behavior of the titanium alloy Ti-7Al-3Cb have shown that the linear dimensional changes associated with the polymorphic transformation need not be isotropic. The absolute magnitude of the linear dimensional change, which may be either positiue or negative, associated with the cr-p transformation is dependent upon the relutzve volumes of different orientations of the transformation product. It is hypothesized that the dilation irregulati-ties that have been observed during the polymorphic transformation of pure, coarse-grained titanium and other titanium-base alloys can be explained in the same manner. When titanium is heated above about 165O°F, the hcp a structure transforms to bcc 0. Thermal-dilatioh measurements have shown that the transformation is accompanied by a decrease in length of 0.16 pct.&apos; Such dilation behavior would be expected because the volume of the hcp unit cell is about 0.3 to 0.4 pct greater than that of the bcc unit cell. A recent investigation2 of the thermal-dilation behavior of an experimental a-p* titanium alloy, Ti- 7A1-3Cb, containing 0.06 wt pct 0 showed that its dilation behavior during the polymorphic transformation differed substantially from that reported for unalloyed titanium. The first time the alloy was cycled through the transformation, the dilation curve closely duplicated that of unalloyed titanium. However, upon repeated cycling through the transformation temperature range, both the magnitude and the sign of the dimensional change associated with the transformation were observed to vary with each cycle. This investigation was undertaken to obtain additional data on the dimensional changes associated with the polymorphic transformation in the Ti-7A1-3Cb alloy and to determine the cause of the dimensional irregularities. After testing, the specimens were examined metallo-graphically. In addition, Laue back-reflection patterns were obtained from selected sections taken perpendicular to the specimen axes to determine the a orientations present in these sections. White radiation from a tungsten target and a 0.1-mm-diam collimator were used to produce the diffraction patterns. RESULTS Dilation Curves. Three types of thermal-dilation curves were obtained when the a-8 titanium alloy was heated and cooled through the transformation temperature range. These three types of curves are illustrated in Fig. 1. The type I curve represents what is considered normal behavior, because the dilation change is what would be expected on the basis of the volumes of the unit cells of a and p. The Type I1 curve is the inverse of Type I. Normal behavior is characterized by an expansion on cooling through the transformation, whereas a contraction takes place in the Type 11 curve. With Type ni behavior, no clearly distinguishable length change occurs during the transformation. No other anomalies that might be indicative of other phase transformations were observed in the dilation curves at lower temperatures. Apparently, the cooling rate was low enough for equilibrium to be reached during the 0 to a transformation. Table I lists the types of dilation curves observed during the polymorphic transformation as a function of the direction of measurement and cycle number. The A1 value was determined by extrapolating the low-temperature (a + 5 pct p) and high-temperature (100 pct p) segments of the dilation curves to a common temperature and measuring the difference in the or-dinates at that temperature, see Fig. 1. The transformation occurs over a temperature range in this alloy, so the magnitude of A1 is not an absolute value but depends on the choice of temperature. A mean temperature, T,, within the transformation temperature range was selected for the measurement. T, on cooling occurred about 100°C lower than T, on heating. The first time each of the three dilation specimens was heated to above the temperature, that is, Cycle 2, normal Type I behavior was observed. In Cycle 3, two deviations from normal behavior occurred. First, during cooling of the longitudinal specimen, a substantially larger expansion, +0.21 pct, was measured as 0 transformed to a compared with +0.03 pct in Cycle 2. Second, the thickness specimen was observed to undergo a contraction instead of the anticipated expansion on cooling. Continued cycling of the three specimens from room temperature to 2500°F produced additional changes in the dilation behavior. These changes did not seem to be related to the fabrication direction of the alloy because the values of a1 for the longitudinal, transverse, and thickness specimens varied unpredictably in magnitude and sign. Furthermore, both the longitudinal and transverse specimens showed all three types of dilation curves at least once during the six cycles that they received. Fig. 2 is a sketch of the transverse specimen after

Jan 1, 1967

By W. F. Campbell

One of the deepest coal operations today is the Springhill No. 2 mine of Cumberland Railway & Coal Co., subsidiary of Dominion Coal Co. Ltd. Mining is now conducted at a slope distance of 14,000 ft, with 4400 vertical ft of cover. The record of Springhill No. 2 can be said to contain the history of bumps in the Province of Nova Scotia. The Springhill coal field forms part of the Cumberland field of Carboniferous age. There are seven mineable fields in the area, numbered in the order they were discovered. Mining has been carried on in all but the No. 4 and 5 seams, but present operations are confined to the No. 2. Fig. 1 shows a vertical section through the seams. Opened in 1873, No. 2 mine was first worked from parallel slopes driven from the outcrop of No. 2 seam down to the 7700 level. As the mine went deeper, a two-place auxiliary slope was driven from the 6900 level to the present workings. A transfer level at the 7800 connects the main haulage with the auxiliary haulage slope. The No. 2 mine plan is shown in Figs. 2 and 3. The seam is bituminous, averaging 8.5 to 9 ft thick. There is a well defined parting 14 to 16 in. from the roof, and this roof coal is harder than the rest of the seam. Average pitch at the outcrop is 30°; at the 6500 level, 20°; at the 7900 level, 16°; and at the 13,800 level, 10°. Immediate roof and floor strata consist of beds of variable thicknesses of shales, grading to arenaceous shales to shaly sandstones to sandstones. A characteristic of the strata is the appearance and disappearance of sandstone bands, of considerable thickness, over distances of several hundred feet. MINE HISTORY Entrance to No. 2 mine is obtained by three parallel slopes, separated by 100-ft pillars except in the upper portion of the mine where the pillars are smaller. Main haulage levels were originally driven 600 ft apart for room and pillar extraction. A parallel drainage and intake airway was driven below each haulage level and a parallel return airway (counter level) above. Pillars 80 to 100 ft wide separated these two servicing entries from the center haulage level. Inclines up to 700 ft apart were driven off the levels up pitch to the upper levels, and at 40-ft centers level rooms 12 ft wide were driven off each side of the inclines, separated by crosscuts every 50 to 100 ft. The rooms were driven up to 350 ft or until they were holed into the room from the adjoining incline—a plan followed until the level reached its boundary. When the entire area between two levels had been divided into pillars, the pillars were extracted from the boundary back to the slope pillars. As depth of cover increased, mining conditions required larger pillars, and at the 3300 level, where NECESSARY PRECAUTIONS FOR MINING AT DEPTH In Room and Pillar Extraction: 1) Pillars must not be too small. 2) Pillar size must be uniform. 3) Extraction lines must be kept as straight and as uniform as possible. If they are irregular they should be brought back into line slowly. 4) Peninsulas of coal surrounded by gob must be avoided. 5) Pillars should not be disturbed after they have been formed. If it is necessary to increase the width of an opening, stripping or ribbing should be done gradually over a long distance. If increased width of openings is necessary at certain locations and can be anticipated, the openings should be widened during development. 6) Under no conditions should small pillars be left in the gob that would interfere with caving. In Long wall Operations: 1) Pillars formed during development for retreating longwalls should be uniform in size and shape. 2) Pillars should not be split after development, but if pillar splitting does become necessary it should not be carried out within the zone influenced by the working faces. 3) Width of levels should not be increased after the levels have been developed. If it does become necessary to widen a level it must be done gradually over a long distance by stripping or ribbing the coal ribs. 4) Extraction lines should remain uniform. If several walls are worked together—one behind the other—a uniform distance must be maintained between them and the wall faces must be kept as straight as possible. If the walls do get out of line, they must be brought back into line gradually to allow for a gradual change in the stress distribution over the area. 5) Stumps of coal, roof supports, etc. must not be allowed to remain in the gob to interfere with caving. 6) Midwalls should be built as rigidly as possible and properly maintained.

Jan 1, 1959