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By N. I. Fisher, J. Shepherd

Abstract-Statistical studies have been carried out on structural geological data collected across a large zone of roof failure 600 m (1968 ft) wide and at least 800 m (2642 ft) long in the Greta coal seam at Aberdare East Colliery. Two swarms of hundreds 2 of minor, normal faults with throws commonly between 3 and 300 mm in the room and pillar workings are broadly coincident with roof failure. The faults have been classified into dip slip and oblique and strike slip types. Roof conditions have been classified into good; troublesome with subclasses scaly, heavy, gutter falls and wide, flat-roofed falls; and severely failed with subclasses very heavy roof, gutter falls and dome falls. Troublesome conditions are defined as those in which the height of the fall is less than or equal to 0.3 m, and severely failed conditions as those in which the fall height is greater than 0.3 m. Comparison of faults, roof conditions and mining rate on a shift basis indicates that faults and roof failure are much more important than machine breakdowns in reducing mining rate. The effect of faults on roof conditions has been quantified using a concept called the "zone of influence, " a rectangular area around a fault in which the fault has potentially deleterious effects. The spatial comparison of fault "zones of influence" with areas of roof failure using Spearman's rank correlation coefficient shows that, while normal dip slip faults do not appear to be associated with roof failure, oblique slip and strike slip faults appear to be associated with roof classed as severely failed. The "zone of influence" of an oblique slip fault may extend up to 3 m on each side of it in the headings and up to 1.14 m in the cut-throughs. The fault "zone of influence" has geomechanical implications for the design of mine openings and possibly represents the maximum length of a cantilevered roof beam likely to fail during mining, owing to a fault. Roof conditions could possibly be predicted in blocks of virgin coal if the type of fault could be identified in oriented drill cores.

Jan 9, 1978

By N. I. Fisher, J. Shepherd

Statistical studies have been carried out on structural geological data collected across a large zone of roof failure 600 m (1968 ft) wide and at least 800 m (2642 ft) long in the Greta coal seam at Aberdare East Colliery. Two swarms of hundreds of minor, normal faults with throws commonly between 3 and 300 mm in the room and pillar workings are broadly coincident with roof failure. The faults have been classified into dip slip and oblique and strike slip types. Roof conditions have been classified into good; troublesome with subclasses scaly, heavy, gutter falls and wide, flat-roofed falls; and severely failed with subclasses very heavy roof, gutter falls and dome falls. Troublesome conditions are defined as those in which the height of the fall is less than or equal to 0.3 m, and severely failed conditions as those in which the fall height is greater than 0.3 m. Comparison of faults, roof condition and mining rate on a shift basis indicates that faults and roof failure are much more important than machine breakdowns in reducing mining rate. The effect of faults on roof conditions has been quantified using a concept called the "zone of influence," a rectangular area around a fault in which the fault has potentially deleterious effects. The spatial comparison of fault "zones of influence" with areas of roof failure wing Spearman's rank correlation coefficient shows that, while normal dip slip faults do not appear to be associated with roof failure, oblique slip and strike slip faults appear to be associated with roof classed as severely failed. The "zone of influence" of an oblique slip fault may extend up to 3 m on each side of it in the headings and up to 1.14 m in the cut-throughs. The fault "zone of influence" has geomechanical implications for the design of mine openings and Possibly represents the maximum length of a cantilevered roof beam likely to fail during mining, owing to a fault. Roof conditions could Possibly be predicted in blocks of &gin coal if the type of fault could be identified in oriented drill cores.

Jan 1, 1979

By A. Szirmae, Hsun Hu

The early stages of recrystallization in a 70 pct cold-rolled Si-Fe crystal of the (110) (0011) orientation were studied with a Siemens electron microscope. Orientation studies based on electron-diffractzotz. patterns confirm the results of previous texture analysis. The driving energy for recrystallizatior and the critical radius for growth were calculated from the dislocation energy and the energy of the subgrain bourzdaries, and it was found consistent with the observed size of the recrystallized grains. The recrystallization characteristics of crystals with different initial orientations are discussed. The recrystallization of cold-rolled (110)[001] crystals of Si-Fe has been widely studied by various investigators.1-4 Their results on both deformation and annealing textures are in good agreement. The rolling texture after 70 pct reduction consists mainly of two crystallographically equivalent (111) [112] type textures and a minor component of the (100) [011] type. The latter is derived from the deformation twins, or Neumann bands, which are formed during the early stages of deformation and later rotate to the (100) [011] orientation upon further rolling reduction. Between the two main (111) [112] type textures, there is some orientation spread, because of which very low intensity areas appear in the pole figure. If these very low intensity areas are considered to be a very weak component in the texture, then a (110) [ 001 ] orientation may be assigned to them. When this rolled crystal is annealed at a sufficiently high temperature for recrystallization, the texture returns to a simple (110) [001]. The purpose of the present investigation was primarily to seek a better understanding of the recrystallization process by using the electron transmission technique. The (110) [0011 type of crystal was selected because orientation data for it are well known from previous studies with conventional techniques. Direct observations on the recrystallization of such a crystal have also been made by using a hot-stage inside the electron microscope, and the results will be reported in another paper. MATERIAL AND METHOD A single-crystal strip of the (110) [001] orientation was prepared from a commercial grade 3 pct Si-Fe alloy by the strain-anneal technique.= The strip was approximately 0.014 in. thick, and was rolled 70 pct at room temperature to a thickness of 0.004 in. Specimens were cut from the rolled strip and were annealed in a purified hydrogen or argon atmosphere. They were then electrolytically polished in a chromic-acetic acid solution to very thin foils. Best results were found by polishing first between two narrowly spaced flat cathodes with the specimen edges coated with acid-resisting paint, followed by polishing between two pointed electrodes until a hole appeared in the center as described by Bollmann.6 It was found that a thin transparent film always formed along the thin edges of the polished specimen. This film was then removed by rinsing the specimen very briefly in a solution of alcohol with a few drops of HF or HCl. RESULTS AND DISCUSSION 1) The Deformed Crystal. From the electron-diffraction patterns taken at various areas of an as-rolled specimen, the texture components as deduced - from ordinary pole-figure analysis were confirmed. Over most of the areas where orientation was examined, a (111) pattern with a [112] direction parallel to the rolling direction was obtained. This corresponds to the main deformation texture of the (111) [112] type. In a few areas the diffraction pattern was (100) [Oil], corresponding to the minor-texture component derived from the Neumann bands. The (110) [001] orientation, which corresponds to the very weak intensity area in the pole figure, was found infrequently. A typical example of the deformed matrix having the (111) type main texture is shown in Fig. 1, where (a) is the microstructure and (b) is the diffraction pattern taken from that area. It was also frequently observed that in other areas more or less continuous rings of weaker intensity were superimposed on the simple (111) diffraction pattern, suggesting the presence of a wide range of additional orientations. Other evidence indicated that the recrystallization characteristics are different in these two different types of areas. The hot-stage observations which provide this evidence will be discussed in another paper. AS shown in Fig. l(a), numerous dislocation-free areas of very small size are embedded in the "clouds" of high-dislocation density. This indicates that the deformation of a single crystal, even after a rolling reduction of 70 pct, is far from uniform on a micro-

Jan 1, 1962

W. H. Blauvelt, New York, N. Y.—One thought lias been running through my mind during the wholc of this meeting and that is that the scientific and the practical men must recognize very clearly their interdependence. The value of scientific classification of coal is going to be of the very greatest importance to the users, the practical men. Is not the scientific investigation and the great amount of work that is being done in a measure at least lost to the world? Therefore the scientific investigations and the practical needs of the users should bo brought as close together, and the work should be done as closely together, as possible; that is, the scientific man should know what the practical man needs, and the practical man should not feel that the scientific man is merely a theorist. Scientific investigation is going to have a great effeet and be of great valuc to the practical man who is trying to solve his problems. In the subject which I discussed' for instance, we must look to the scientific man to tell us why coal cokes in one way and not In another and why certain coals will do certain things and others, which appear on the surfacc to be generally similar, do not act in the same way. Need or Physical Data on Coal H. J. Rose, Pittsburgh, Pa.—There is a subject which is a sort of hobby of mine; that is, the need for what might be called critical tables of constants for coal. The chemist has big volumes giving constants, such as the density, solubility, specific heat, thermal conductivity and all other physical and chemical data that have been determined for chemical compounds. Data arc also available on many common materials, for example, the density, hardness, modulus of rupture or maximum crushing strength of swamp white oak as compared with some other wood. In fact, physical data for practically cvery hype of wood commercially produced in the world can he found. In the same way the metallurgical man has handbooks giving the properties of alloys, etc., but we havc very little tabulated information about coal. Our principal reference works are the volumes published by the U. S. Bureau of Mines on the proximatc and ultimate analysis and calorific values of coals of the United States. That is 3 pioncer work of enormous value, but we have reached the point where we need more diversified information. Mr. Fulweiler raised the question of the relative strength of the different coals and cokes. Dr. Campbell and Dr. Ashley wanted to have some information on the resistance of coal to air slacking. It was brought out in the discussion that we want to know something about the coking properties of coal. There are any number of physical tests that we need, such as the thermal conductivity of certain coals, the coefficient of expansion, or the coefficient of friction; or other constants. A smattering of such information is scattered through the literature; for instance, a research worker in Wales will report a coefficient of expansion on Wclsh coals and one in South Africa will report something else for one or two kinds of African coals, hut it is difficult to find the information that is needed on our own coals. Would it not be worth while to consider collecting reliable critical

Jan 1, 1930

By Robert H. Merrill, David W. Wisecarver, Raymond M. Stateham

The US. Bureau of Mines, in cooperation with US. Borax and Chemical Corp. and Kennecott Copper Corp., has investigated the use of the microseismic method to evaluate the stability of large, open-pit slope walls. The method is based on the phenomenon that stressed rock normally emits subaudible rock noises, and the number of rock noises per unit time (noise rate) and the magnitude of the rock noises (amplitude) increase as the stresses in the rock approach the failure stress of the rock. Therefore, the detection and recording of those rock noises serve as a semiquantitative method of predicting the incipient failure of rock. This report briefly describes the three different types of micro-seismic apparatus, the procedures, and the results of microseismic investigations in the slope walls of the Boron mine near Boron, CaL, and the Kimbley, Liberty, and Tripp-Veteran open-pit mines near Ely, Nev. Microseismic monitoring within a frequency band of SO to 5000 Hz indicates noise rates in stable, inactive mining areas are between 0 and 10 noises per hour; the rates in stable, active mining areas are between 10 and 50 noises per hour; and the rate in unstable areas is as high as 2500 noises per hour. High microseismic noise rates in the Liberty pit correlate with the time of nearby earthquakes, indicating that the earthquakes affected the slope wall. The results provide evidence that the microseismic technique is applicable to large pit walls, and that the wide-band, wide-range microseismic equipment appears to be suitable for open-pit investigations. The microseismic method is based on the phenomenon that stressed rock normally emits subaudible rock noises, and the number of rock noises per unit time (noise rate) and the magnitude of the rock noises (amplitude) increase as the stresses in the rock approach the failure stress of the rock. Therefore, the detection and recording of those rock noises serve as a semiquantitative method of predicting the incipient failure of rock. The method has been used for many years to detect incipient failure in roofs or pillars in underground mines. In 1963 the U.S. Bureau of Mines (USBM) started an investigation of the microseismic method in large, open-pit slope walls. The purpose of this investigation was to evaluate the method in open-pit slopes where the rock may be fractured and broken and where the size of the rock mass under investigation is much larger than normally encountered underground. In addition, both the stresses in the rock and the strength of rock near pits are lower than usually found underground. Consequently, there was some doubt concerning the feasibility of the method for open pits, and the economics of such an investigation may have been prohibitive especially if large walls had to be monitored with closely spaced geophones. The successful application of the microseismic method to underground operations has improved safety at little, or no sacrifice, to production or extraction ratios. The anticipated reward in open-pit mining would be the improvement of safety with a minimum sacrifice to mining operations. There is also a possibility that the method could be used to optimize the unloading (stripping) of potential failure areas by the removal of intact rock from the slope wall rather than the cleanup of a slide from the bottom of the pit. This report contains a brief description of three types of microseismic apparatus used in four different pit walls, each of which is different in height, slope, rock types, or has different planes of weaknesses, such as faults, fractures, or joints. Because the geologic features of the pit walls are varied and complex, for brevity, this report dwells mostly on the microseismic apparatus, techniques, the rock noise rates, and the slope movements measured at the various sites. PROGRESS AND DEVELOPMENT The microseismic method was developed over 20 years ago; and the method and examples of investigations in underground mines are summarized by Obert and Duvall. 1 In more recent years, the method has been applied in several underground mines, and an in-situ test under controlled stress conditions is described by Morgan and Merrill. 2 Experience has shown that, on occasions, the microseismic noise rate and amplitude reach a peak value and then start to decrease before a failure occurs in an underground mine; on other occasions, the noise rate steadily increases to a maximum at failure. The method has been applied to slopes by Goodman and Blake,3 and by Paulsen. 4 Goodman and Blake found that the noises corresponded with failures in the slope

Jan 1, 1970

By H. N. Hall

Various factors must be considered in an engineering evaluation of gravity-drainage reservoirs. Among these are: (1) the effect of producing rate on total oil recovery; (2) the effect upon well productivity and ultimate recovery of the pressure level maintained during the producing life of the reservoir; (3) the economic advantage of full or partial pressure maintenance; and (4) estimate of the rate of gas production and injection and the possible purchase of gas under conditions of full pressure maintenance to ascertain compressor facilities needed. All of these factors can be evaluated only when a reliable method is employed for determining reservoir performance in gravity-drainage reservoirs. The purpose of this paper is to present a general method for calculating the performance of a gravity-drainage reservoir. This method is applicable for conditions of complete pressure maintenance, partial pressure maintenance and normal pressure depletion. Provisions are made to take into account variations throughout the reservoir of reservoir configuration, changes in permeability and fluid composition. Based on the method presented in this paper, an IBM 650 computer program has been developed. The past performance of an actual gravity-drainage reservoir producing under conditions of declining pressure and no gas injection was duplicated using this program. INTRODUCTION In tilted reservoirs the production of oil is influenced by drainage of oil from upstructure to downstructure locations. When this downstructure drainage of oil is sufficient to cause effective segregation of the gas and oil in a reservoir, the reservoir is usually classified as a segregation drive or gravity-drainage reservoir. (Discussion will be restricted to gravity-drainage reservoirs which have no encroachment of edge water.) The important feature in gravity-drainage reservoirs is the density difference between reservoir oil and gas. These phases tend to segregate in the reservoir with the result that in the gas cap the oil saturation is maintained at a higher level by drainage of oil from the gas-cap area. Oil can be produced from the oil zone at a low gas-oil ratio and reservoir energy is thereby conserved. The standard material balance in not adequate for predicting gravity-dramage reservoir performance because it does not take into account the difference in saturation above and below the gas-oil contact. Several authors'.' have presented methods for calculating the performance of gravity-drainage reservoirs in which reservoir pressure is maintained constant by gas injection into the gas cap. Using some simplifying assumptions, these methods can be employed with a desk calculator to give acceptable results. The problem of predicting the performance of gravity-drainage reservoirs under the conditions of declining reservoir pressure is many time more complex than that of constant pressure. fierefore, attempis to develop a method suitable for desk calculation have required excessively simplified assumptions. In the past several years, highspeed digital computers have become more widely available for reservoir engineering problems. These corn puters are well suited to problems such as the prediction of the performance of gravity-drainage reservoirs with pressure decline. Many of the simplifying assumptions necessary for hand computation can be eliminated so that a realistic approach to the gravity-drainage process can be made. CONCEPTUAL PICTURE OF OIL MOVEMENT IN GRAVITY-DRAINAGE RESERVOIRS Before attempting to develop an analytical treatment for conditions occuring in a gravity-drainage reservoir, a concept should be formed concerning the movement of fluids in the reservoir as oil is produced. A review of the literature'.' shows that it is customary to classify gravity-drainage operations into two categories—(1) with complete pressure maintenance, and (2) with declining pressure. The same line of reasoning will be followed in presenting the concept of the movement of fluids in the reservoir because it is easier to visualize the movement of fluids under conditions of complete pressure maintenance. After discussing complete pressure maintenance, an analogy will be made between that and the case of declining pressure. It should be kept in mind throughout that the final aim for the problem of solving gravity-drainage performance with digital computers will be to develop a general program for any kind of gravity-drainage reservoir. COMPLETE PRESSURE MAINTENANCE One feature which is generally common in gravity-drainage reservoirs is a gas cap located at the top of the structure. This is shown in Fig. 1(a). Fig. l(b) shows oil saturations that might occur through the reservoir. In the gas cap, oil saturation is lower than

By A. Lawley, H. W. Schadler

TWINNING has long been recognized as a possible mode of deformation in crystalline solids and has been studied in a wide variety of crystals.&apos; Recently, deformation markings which have the topographical characteristics of twins have been seen in tungsten" and the body-centered cubic alloys of tungsten and molybdenum with rhenium.3-7 These markings have been identified as twins because: 1) they are visible after polishing and etching;2,3 2) their formation is accompanied by an audible click and a drop in load;4 and 3) the habit plane is {112}, the plane which has been identified as the twinning plane for several body-centered cubic metals.&apos; However, there has been no published evidence for the specific determination of the twinning direction in rhenium alloys of tungsten and molybdenum, because usually the deformation twins were not broad enough to be detected with a conventional X-ray beam. Consequently, [111] is inferred as the twinning direction since the latter must lie in a plane of symmetry perpendicular to the twinning plane (112). As Sims and Jaffee3 and Lawley and Maddin4 have shown, the addition of rhenium to molybdenum and tungsten increases the ductility of the alloy over that of the pure metal, but twinning is much more profuse in these alloys than in the pure elements, particularly at Mo-35 pct Re*and W-30 pct Re. Since twinning is often associated with brittle fracture in iron8 and the silicon-irons,9 direct experimental proof that the deformation markings in tungsten and molybdenum alloys of rhenium are twins seemed to be needed. Using the Laue back-reflection technique, the deformation markings in a Mo-35 pct Re alloy are shown to be deformation twins. The twins have a (112) habit plane and the twinning direction is <111>. The Mo-35 pct Re specimen used was taken from a 0.060-in. zone-refined single crystal deformed 6 pct in tension at 78°K. The Laue back-reflection technique, with a film to specimen distance of 2 cm, and white radiation from a copper target were used.

Jan 1, 1962

By J. W. Clark, C. T. Sims

Wrought chromium-base alloys containing yttrium, cubic monocarbides of the Ti(Zr)C type, and similay alloys containing manganese and rhenium have been melted and fabricated. Strength has been studied by hot hardness and elevated-temperature tensile and rupture measurements, low-temperature ductility by tensile testing, and surface stability by oxidation testing. In additiod, studies have been conducted of the carbide stability, and of aging behavior. The carbide dispersion generates effective elevated-temperature strength, which is further enhanced hv strain-induced precipitation. The dispersion exhibits classical dissolution and aging response. The ductile-to-brittle transition temperature of these alloys is above room temperature. The alloys reported show fairly good oxidation resistance, but nitrogen contamination can cause fortnation of a hard Cr2N layer under the oxide scale. Manganese does not appear to be a promising alloying element in chromium. In the years 1945 to 1950, the metal chromium was considered as a possible base for alloy systems due to its considerably higher melting point than superalloys, its low density, its high thermal conductivity, and its apparent capacity for strengthening. However, this interest in chromium was short-lived. It was found difficult to melt and cast, to be exceptionally sensitive to the effect of minor imperfections, to have a lack of ductility at both room and elevated temperatures, and to be subject to a deleterious effect of alloying elements upon the ductile-to-brittle transition temperature.&apos; Since then, chromium, as a practical alloy base, has remained virtually unstudied. Further, purposeful ignoring of chromium has been promoted by statements that its bcc structure would not allow it to be strengthened to useful values, when compared to the "austenitic" alloys.2 Recently, a new look has been taken at chromium-base alloy systems. Study of the literature will show that chromium, providing some of its disadvantages could be eliminated or minimized, actually has a rather attractive potential as an alloy-system base. Analysis of rather scattered data suggests that chromium is quite capable of being strengthened to high levels. Also, significant strengthening of its two sister elements in Group VI-A, molybdenum and tungsten, has been demonstrated in a number of commercial and exploratory alloys. Chromium should be similar. Since chromium does not readily form a volatile oxide like tungsten or molybdenum, it offers a much higher probability of giving birth to alloy systems with useful oxidation resistance. Concerns about possible high elemental vapor pressure have been mitigated by recent data.3 In addition, the physical properties exhibited by chromium are attractive for application as a high-temperature structural material. For instance, its thermal conductivity varies from 49 to 36 Btu-ft/hr-sq ft-°F over its range of usefulness (which is two to four times higher than most superalloys), its density is about 7.2 g per cc (20 pct less than most nickel-base alloys), its coefficient of thermal expansion varies from 4 to 8 x 10-6 per OF, and it has a relatively high modulus of elasticity, approximately 42 x 10&apos; psi.4 Alloying studies on a chromium base in the past have usually encompassed rather sweeping solid-solution alloy additions for strengthening. This is not consistent with contemporary alloying practice in Group VI-A. For instance, molybdenum, also in Group VI-A, is primarily alloyed for strength improvement by use of heat-treatable carbide dispersions.5 Chromium and molybdenum are similar in their chemical activity and other properties. Thus, strengthening of chromium by carbide dispersions was studied. Chromium-base alloys are plagued with room-temperature brittleness, although high-purity unal-loyed chromium can be made ductile.4,8 Use of yttrium as a scavenger has done much to improve ductility and resistance to nitrogen embrittlement in chromium systems,7 so it was utilized in this program. It has also recently been found8 that small rhenium additions (1 to 5 pct) create improvement in the ductility of Type 218 tungsten wire. This is apparently related to the remarkable effect of rhenium additions near its terminal solid solubility in all Group VI-A metals.9&apos;10 Investigation to establish if dilute concentrations of rhenium would also be effective in chromium appeared to be logical for this program. Since rhenium is too expensive to be practical in alloys for application as structural components, ductility improvements through solid-solution alloying were also sought by substitution of manganese for rhenium; manganese, like rhenium, exists in Group VII of the periodic system. The optimum amount of carbide dispersion for chromium-base alloys was obtained by analogy with molybdenum. Strengthening in molybdenum is achieved by use of Ti-Zr carbide dispersions. A

Jan 1, 1964

By H. D. Kessler, M. Hansen, R. J. Van Thyne

The phase diagram of the titanium-rich portion of the system Ti-Cr-Fe to 70 pct Ti was established by means of isothermal sections at 900°, 800°, 750°, 700°, 650°, 600°, and 550°C, using arc-cast alloys. An isotherm at 800°C was determined for the section bounded by Ti, TiFe2, and TiCr2. Micrographic analysis was employed as the principal method of investigation, supplemented by X-ray diffraction and incipient melting studies. A ternary eutectoid, ß ? a+ TiCr2 + TiFe, occurs at approximately 8 wt pct Cr, 13 wt pct Fe, and about 540°C. AMONG the first titanium-base alloys in commercial production were the Ti-Cr-Fe alloys. For this reason, the Materials Laboratory, Wright Air Development Center, sponsored an investigation of the system. No information on the constitution of the titanium-rich corner was available. Vogel and Wenderott studied titanium-poor ternary alloys.&apos; As part of this program, the binary systems Ti-Cr and Ti-Fe have been determined previously by the authors.&apos; Other investigators have also studied the binary systems Ti-Cr,3-7&apos; Ti-Fe.³,8-10 Both of the binary systems are characterized by the eutectoid decomposition of the ß phase. Most of the effort of the present work has been concentrated on the titanium-rich corner with compositions of less than 30 pct total chromium and iron content. The determination of isothermal sections was the experimental approach used to obtain the ternary phase diagram. Vertical sections were used to check the consistency of the isothermal sections. While this investigation was in progress, a study of the Ti-Mo-Cr system at Armour Research Foundation disclosed the existence of a high temperature modification of TiCr2 above 1300 °C.11 This allotrope has a hexagonal structure of the MgZn2 type, iso-morphous with TiFe2, whereas the low temperature modification of TiCr2 is cubic," of the MgCu2 type. The existence of allotropy in TiCr2 of course means a more complicated set of phase relationships in this general region than if the phase were monomorphic, as was first assumed. Additional studies were made late in the investigation in order to clarify the part that the hexagonal TiCr2 phase plays in the ternary phase relationships. These will be discussed in a separate section. Because they are of greatest practical significance, the phase relationships in the titanium-rich corner will be presented first, omitting the equilibria involving the hexagonal modification of TiCr2 in an effort to simplify the presentation somewhat. Experimental Procedure Materials: The titanium used in the preparation of the alloys was iodide crystal bar (99.9 pct pure) produced by the New Jersey Zinc Co. High purity chromium and iron were obtained from the National Research Corp. Table I gives the analyses of these materials. Melting Practice: Over 100 alloy ingots weighing 10 to 20 g were melted in a nonconsumable electrode arc-melting furnace. As the techniques are identical to those reported previously,12,13 they will not be detailed here. The ingots were melted in the cavity of a copper melting block insert under a slight positive pressure of helium. No measurable hardness

Jan 1, 1954

By C. S. Matthews, H. C. Lefkovits

Drilling progress is often delayed by sticking of the drill string. The development of preventive and remedial methods has been hampered by incomplete understanding of the sticking mechanism. A recent lahorntory investigation hns indicated that one type of sticking may be attributed to the difference in pressure between the borehole and formation. This paper shows, by means of soil mechanics, that the primary cause for differential pressure sticking is cessation of pipe movement, whereas diflerential pressre and stanrtding time determine the severity of the sticking. The analysis stresses the importance of using low-weight muds with low solids content and low water loss to alleviate diflerential pressure sticking and describes why packed hole drilling, long strings of drill collars, and a large deviation from the vertical are conducive to sticking. Finally, preventrve and remedial methods ore evaluated, and a theory is presented on the release of stuck pipe by spotting oil. INTRODUCTION Since drilling with long strings of oversize drill collars has become standard practice in many areas, the incidence and severity of the stuck pipe problem has increased. It has been noticed that in the majority of these cases the sticking could not possibly be attributed to key seating or caving of shales. It appeared that, due to the differential pressure between the mud column and the formation fluid, the collars were pressed into the wall and so became "wall stuck". Points to note about differential pressure sticking are: (1) sticking is restricted to the drill collars, (2) the collars become stuck opposite a permeable formation, (3) the sticking occurs after an interruption of pipe movement, (4) circulation, if interrupted, can be restarted after the sticking is noticed, and (5) no large amounts of cuttings are circulated out after restarting circulation. Helmick and Longleyl investigated pipe sticking by differential pressure in the laboratory and found an empirical relationship between the differential pressure, the sticking time and the required pull-out force. In this paper an explanation of the mechanism is given based on Terzaghi&apos;s theory of clay consolidation. A qualitative description is given in the following paragraphs while the derivation of fonnulas is given in Appendices. This paper is a first attempt to explain pressure differential sticking and many points will require additional theoretical and practical investigation before the problem can be fully understood. PRESSURE DIFFERENTIAL STICKING AS A CONSOLIDATION PROBLEM In any borehole, where the mud pressure is higher than that exerted by the formation fluids, a mud cake is formed opposite the permeable sections of the hole and a continuous flow of filtrate takes place from the mud, through the cake and into the formation. This radial flow pattern requires a certain distribution of the hydraulic and the effective (grain-to-grain) stresses inside the mud cake. Any quantitative or qualitative change in the external pressure conditions will produce a change in the flow pattern and, consequently, also in the internal stress distribution inside the cake. In view of the low permeability and the high compressibility of a clay mud cake, the adjustment of the internal stress distribution is slow and is accompanied by a change in volume. Time dependent stresses are thus created which gradually diminish as the new state of equilibrium between internal and external pressures is approached. Some 30 years ago, Terzaghi developed his "Theory of Consolidation" to account for the time-dependent stresses and settling of clay formations under the influence of external loads. He derived a differential equation by which the time-dependent hydraulic stress and the consolidation can be computed for any point inside the layer during the consolidation process. His theory is based on the assumption that the change in stress is solely due to a change in water content and it may only be applied to one-dimensional consolidation phenomena. Other investiga-tors5,10 have expanded his theory to include processes of more than one dimension. The difference between the external pressures on the mud cake before and after sticking is a qualitative one (isolation of part of the cake by the static contact with the drill collars after pipe movement has been stopped)&apos;, and the time-dependent stresses thus created may be investigated by means of Terzaghi&apos;s theory. By this analysis the changes in the nature of the contact surface between the drill collars and the mud cake during the sticking can be explained; and the friction force between the two may be computed as a function of the sticking time, the borehole dimensions and the mud cake characteristics.

By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies&apos;, the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,&apos; vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell&apos; published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson&apos; has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

By S. C. Sun, John A. L. Campbell

The surface properties exhibited by bituminous coal and bituminous coal lithotypes were ascertained by using streaming potential techniques. The electro kinetic prop-erties wereascertainederties of bituminous coal were found to be similar to those of anthracite. The principle electrokinetic properties of the coal and lithotypes, zero-points-of-charge (ZPC), and potential determining ions, were established. The effects of indifferent electrolytes, hydronium and hydroxyl ion sources, and polyvalent ions (cationic and anionic) were also evaluated. Location of the ZPC&apos;s with respect to pH is discussed in terms of chemical and mineralogical composition of the respective surfaces. To account for the observed electrokinetic phenomena, a generalized surface model and adsorption mechanism are proposed. Surface-dependent processes, such as froth flotation and flocculation, are important or potentially important techniques for combating some of the current major problems in coal preparation. In order to correctly apply or improve a surface-dependent process, it is of paramount importance to understand the interfacial phenomenon, especially the double layer properties, exhibited by the solid. The specific objective of this research was to determine the properties of the bituminous coal/liquid interface by an electrokinetic method, streaming potential, and to relate the findings, wherever possible, to the existing unit operations of froth flotation and floccula-tion tion. The electrokinetic properties of both the whole coal and its lithotypes were investigated. As part of the total investigation, the role played in the double layer by the reagents commonly employed in the surface dependent process was also established.&apos; These data will be presented at a later date. Experimental Procedures The coal samples used in this research and their designations are listed in Table 1. The classical description of humic coal lithotypes as developed by Stopes" was used for the delineation of the lithotype samples. The samples were taken from the working face of a producing deep mine of the Pittsburgh seam in the area of Ellsworth, Pa. To avoid oxidation, only freshly exposed areas were sampled. The normal precautions against contamination were also exercised. Two types of samples were taken, specimens rich in a particular lithotype and a representative channel sample. The latter sample was prepared for analyses by grinding it to —35 mesh. It was screened repeatedly during the grinding to provide the largest amount of 35 x 48-mesh (standard Tyler sieves) material possible. The screened fraction was passed over a magnet and then washed several times with distilled water and finally with conductivity water. The resulting sample now termed "whole coal" was stored under conductivity water in a glass bottle. Pure lithotypes were obtained from the lithotype concentrates by hand picking, and were processed in the same manner as the representative sample. Maceral analyses, employing standard petrographic procedures," were performed on the lithotype samples to determine the purity of the samples. The results are presented in Table 2. Reflectance measurements of the vitrinites and fusinites are also reported in this table. Proximate and ultimate analyses of the samples are given in Tables 3 and 4. The electrokinetic properties of the coal samples were determined by streaming potential methods.&apos;-&apos; All of the chemicals used in the investigation were reagent grade (Baker analyzed). The conductivity water was prepared by doubly distilling the water in a pyrex Yoe-type still and passing the distillate through a mixed bed ion exchange column. Results In general, the electrokinetic properties of the investigated bituminous coal were found to be similar to the results of a previous study of anthracite by Camp-bell bell5 and are in accord with the suppositions of Brown." The zeta potentials of the coal and all the lithotypes were found to be negative in conductivity water. Jowett? in a study of slime coatings on coal also found bituminous coal to exhibit a negative surface. Fig. 1 shows that the negative charges, at neutral pH&apos;s, for both fusain and the gangue are very small, almost zero, while at the same pH, vitrain has the largest negative charge, almost 30 mv. Durain has a negative charge of 17.5 mv. The determination of the affect of pH on the charge of the coal surfaces revealed that hydronium and hydroxyl ions apparently behave as potential determining ions; however, they do not appear to be potential determining for the gangue. These results are illustrated in Fig. 1. As the pH of the solution was decreased, hydronium ions were adsorbed, causing the surface of the coal to reverse polarity and become

Jan 1, 1971

By O. C. Baptist

The Umiat oil field is in Naval Petroleum Reserve No. 4 between the Brooks Range and Arctic Ocean in far-northern Alaska. The Umiat anticline has been tested by 11 wells, six of which produced oil ; however, [lie productive capacity and recoverable reserves of the field are subject to considerable speculation because of unusual reservoir conditions and because several wells appear to have been .seriously damaged during drilling and completion. Oil is produced at depths of 275 to 1,100 ft; the depth to the bottom of the permanently frozen zone varies from about 800 to 1,100 ft, .so that most of the oil reserves are in the permafrost Reservoir pressures are estimated to range from 50 to 350 psi, increasing with depth, and the small amount of gas dissolved in the oil is the major source of energy for production. Laboratory tests were made on cores under simulated permafrost conditions to estimate oil recoverable by solution-gas expansion from low saturation pressures. The cores were also tested for clay content and susceptibility to productivity impaiment by swelling clays and increased water. content if exposed to fresh water. The results indicate that oil can be produced fronz reservoir rocks in the permafrost and that substantial amounts of oil can be produced from depletion-drive reservoirs by a pre.s.r~lrr drop of as little as 100 psi below the saturation pressure. Freezing of formation water reduces oil productivity much more than that due to increased oil viscosity: Failure of we1ls drilled with rtuter-base mud to produce is attributed to freezing of water in the urea immediately surrounding the wellbore. Swelling clays apparently contributed very little to the plugging of the wells. INTRODUCTION Naval Petroleum Reserve No. 4 lies between the Brooks Range and the Arctic Ocean in northern Alaska. The Umiat oil field is located in the southeastern part of the Reserve and is about 180 miles southeast of Point Barrow (the only permanent settlement in the Reserve and the primary supply point for drilling of the wells at Umiat). Eleven wells were drilled for the U. S. Department of the Navy, Office of Naval Petroleum and Oil Shale Reserves, between 1944 and 1953 to test the oil and gas possibilities of the Umiat anticline. Six of these wells produced oil in varying quantities and the best one pumped about 400 B/D.&apos; Estimates of recoverable oil range from 30 to 100 million bbl. The main oil-producing zones are two marine sandstone beds in the Grandstand formation of Cretaceous age: these are referred to as the upper and lower sands. Good oil shows were found throughout the sand settions in the first three wells drilled on the structure, but the highest rate of oil production obtained on any 01 the many tests was about 24 BOPD. These first wells were drilled with conventional rotary methods using water-base mud; later wells were drilled either with cablc tools using brine or rotary tools using oil or oil-base mud. These experiments were successful as is shown by comparing the oil production from Well No. 2 with that from No. 5. These two wells are only 200 ft apart and are located at about the same elevation on the structure. Well No. 2. drilled with a rotary rig using water-base mud, was abandoned as a dry hole after all formation tests were negative. Well No. 5. drilled with cable tools and reamed with a rotary using oil, pumped 400 BOPD which was the maximum capacity of the pump and less than the capacity of the well. These field results indicated that the producing sands were extremely "water sensitive" and it was assumed that the cause of this sensitivity was the presence of swelling clays in the sands. Because of the very unusual reservoir conditions and the difficulties encountered in completing oil wells in the permafrost. the Navy asked the U. S. Bureau of Mines to make laboratory studies under simulated permafrost conditions to assist them in estimating the production potential of the field and the recoverable reserves. These tests were designed to determine the cause of the plugging of wells in the permafrost and to test oil recovery from frozen sand by solution-gas expansion with the oil gas-saturated at very low pressures. EXPERIMENTAL METHODS AND PROCEDURES Samples Analyzed Core samples were analyzed that represent the lower sand in Umiat Well No. 7, the upper sand in No. 3. and both the upper and lower sands in No. 9. These sands should be productive in all of the wells because of their location on the structure. Core samples from

By S. Beatty

RECENT experimental results&apos; on the superconductive properties of vanadium indicate that the magnetic behavior of the metal is greatly affected by internal strains caused by mechanical work, and particularly by oxygen and nitrogen impurities. These result in an increase in the hardness of the metal such that metallurgists&apos; have used hardness as a measure of the impurities. An increase in the impurities should also be reflected in a change of lattice parameter with increasing impurity content. The lattice parameter of vanadium prepared by the thermal decomposition of the iodide has been determined by two workers. Neuburger3 obtained a value of a, =3.0338 ± 0.0003A for the body-centered cubic lattice by means of the powder method. The work of Katelaar is referred to by van Arkel4 in which a value of a0 = 3.025 is given. Four samples were used for this investigation. Sample A, the vanadium of the highest purity in the group, was obtained by means of the thermal decomposition of vanadium diiodide and deposited on a 3 mil diam tungsten filament in the form of crystals. The second sample, labeled B, was obtained by the calcium reduction of the pentaoxide at a sufficiently high temperature to give a melt. A third sample, C, was obtained in the same manner as B but remelted in a pure argon atmosphere. The last sample, D, was prepared by the calcium reduction method and the fine powdered vanadium was then sintered by means of applied heat and pressure. Samples A, B, and C were thus essentially free of mechanical strain in their preparation. Sample D was annealed in a high vacuum at 800°C. The samples were prepared for X-ray diffraction analysis such that all additional strain by cold work or by contamination with oxygen and nitrogen was kept at a minimum. Powder obtained from filings was deemed unsuitable since this would require annealing to get rid of the cold work. A heat treatment up to 1000°C at 10-6 m pressure might still increase the impurity content by means of adsorbed oxygen from residual gas in the vacuum chamber. The most satisfactory samples were prepared for back-reflection film techniques. Samples were cut to size, etched with hydrobromic acid, and mounted in Bakelite. They were then lightly polished on 3-0 paper and lightly etched. Chemical and Hardness Analysis of Samples Spectrographic analyses were made of the four samples and indicated similar metallic impurities for the group. The major metallic impurity in each sample was iron, which was less than 0.01 pct. The sum of the other metallic impurities was approximately 0.1 pct. The carbon content was assumed low by virtue of the methods of sample preparation. The principal impurity difference between the samples was in the oxygen and nitrogen content.

Jan 1, 1953

By D. J. Bourne, G. E. Atwood

The new potash refinery of Duval Sulphur & Potash Co. produced its first tonnage of muriate of potash in November 1951. Full capacity was attained in early 1952. Excellent extraction efficiency is being obtained by the process, which is basically froth flotation. System temperature control is practiced and has proved to be of great metallurgical value through high potassium recovery and. low reagent cost. WHEN Duval Sulphur and Potash Co. recently entered the established potash industry, the vast amount of pioneer work essential in an entirely new endeavor was unnecessary. Thus it was possible to screen and assemble proved techniques into a highly efficient process based on the combined knowledge of the industry. It is hoped that the refinements Duval has added to these cumulative achievements will contribute to the rapid advance of the potash industry and related enterprises. The process selected utilizes as raw material syl-vinite ore typical of the Permian Basin. This ore is principally comprised of interlocked crystals of potassium chloride, about 40 pct, and sodium chloride. Also there is as much as 1 1/2 pct of dispersed clay slime which, because of its nature, highly complicates beneficiation of these ores. The refining method is basically flotation in which the mineral sylvite is floated away from the halite-clay gangue to produce a 60 pct K,O muriate of potash product for the plant-food trade. It departs from established practice in the use of an improved reagent scheme, developed by the company&apos;s technical staff, and in

Jan 1, 1954

By Erwin S. Sperry

The oxidation of metals melted in contact with air takes place with dissimilar results. Tin, lead or zinc are examples of a class, the oxides of which float on the surface of the melted metal. First a film is produced, which covers the surface; then, if agitation from any cause exposes new metal to the action of the air, additional oxidation takes place, and the film is increased in volume. This change goes on until a considerable quantity of oxide (or " dross," as it is technically called) is formed; depending, of course, upon the duration of the exposure of the metal to the atmosphere. When such metals are poured, the dross may be skimmed off; and clean metal will be left underneath. The removal of such oxides is, therefore, merely a mechanical process. In the case of copper, however, the result is quite different. The sub-oxide of copper (Cu2O) is readily soluble in molten copper; and therefore, instead of the formation of a film of oxide, to be finally removed as dross, the surface of the metal remains bright and clear, because the oxide has been dissolved as soon as it was produced. It is customary in the process of copper-refining to leave a small quantity of oxide in the metal, in order to oxidize any traces of bismuth, arsenic or antimony which have not been entirely removed. As a result, these metals exist in the commercial product as oxides, and not as metals, which would form an

Jan 1, 1901

By Howard N. Eavenson

In many of the bituminous-coal districts of this country, more than one seam of workable coal exists, and in most cases the lower seam is the more attractive, owing to either its greater thickness or its superior quality. Apprehension that the mining of a seam will destroy the availability of all overlying seams has hindered the development of many fields and has led to the unprofitable working of certain seams in order to save them from an expected total loss. The U. S. Coal & Coke Co., Gary, W. Va., was the first operator in the Pocahontas field to mine the No. 4 seam extensively, which occurs about 80 ft. above No. 3, the scam that was worked first. This was due to the fact that over large areas the upper seam was the only one of workable thickness, at that time. In two places, both seams were workable in the same area, the No. 4 being thinner and containing more impurities than No. 3 seam. In mining these areas, an attempt was made to keep the workings in the upper seam in advance of those in the lower one, and no pillar robbing was done in No. 3 seam until after pillars in that part of the upper seam directly over it had been mined. This resulted in an excessive development in the lower seam, with large areas of finished rooms and standing pillars. The top fell badly, and after a couple of years the falls became so heavy that pillar drawing was unduly expensive. To overcome this obstacle and allow No. 3 seam to be worked in some territory where No. 4 was thick, but too dirty for present use, a study was made of operating methods applied to superimposed seams in Pennsylvania and Maryland. This was started more than seven yean ago by the writer; his data, supplemented by more recent information gathered by his associates, and by two cases mentioned in recent foreign publications, form the basis of this paper. Central Pennsylvania In central Pennsylvania, the lower coal measures contain several seams of nearly the same thickness but of varying quality, and as mining

Jan 1, 1923

By Howard N. Eavenson

In many of the bituminous-coal districts of this country, more than one seam of workable coal exists, and in most cases the lower seam is the more attractive, owing to either its greater thickness or its superior quality. Apprehension that the mining of a seam will destroy the availability of all overlying seams has hindered the development of many fields and has led to the unprofitable working of certain seams in order to save them from an expected total loss. The U. S. Coal & Coke Co., Gary, W. Va., was the first operator in the Pocahontas field to mine the No. 4 seam extensively, which occurs about 80 ft. above No. 3, the scam that was worked first. This was due to the fact that over large areas the upper seam was the only one of workable thickness, at that time. In two places, both seams were workable in the same area, the No. 4 being thinner and containing more impurities than No. 3 seam. In mining these areas, an attempt was made to keep the workings in the upper seam in advance of those in the lower one, and no pillar robbing was done in No. 3 seam until after pillars in that part of the upper seam directly over it had been mined. This resulted in an excessive development in the lower seam, with large areas of finished rooms and standing pillars. The top fell badly, and after a couple of years the falls became so heavy that pillar drawing was unduly expensive. To overcome this obstacle and allow No. 3 seam to be worked in some territory where No. 4 was thick, but too dirty for present use, a study was made of operating methods applied to superimposed seams in Pennsylvania and Maryland. This was started more than seven yean ago by the writer; his data, supplemented by more recent information gathered by his associates, and by two cases mentioned in recent foreign publications, form the basis of this paper. Central Pennsylvania In central Pennsylvania, the lower coal measures contain several seams of nearly the same thickness but of varying quality, and as mining

Jan 1, 1923

By D. M. Buck

greatly restricted and every effort is being made to do away with it where possible, and to substitute a lead-base babbitt or a babbitt with 50 per cent,. tin. The amount of solder having the composition 50 lead, 50 tin, used by the Pennsylvania Lines East, during 1917, was approximately 100,000 lb., but there is reason to believe that a large portion of this can be replaced by a 60-lead, 40-tin solder with satisfactory results, and instructions have been issued to this effect. Inregard to the quantity of new tin used, it is not possible to give the amount, except approximately and from calculations based on the 1917 consumption of bearing metals by the Pennsylvania Lines East only, it is estimated that about 770,000 Ib. of new tin were required in a total of about 21,380,000 lb. of all kinds of bearing metals turned out by the foundry or purchased in the market. No change has been made in the specifications for bearing metals for some years, as the metals used have been satisfactory. A large proportion of the bearing metals are made up from old material re-melted and brought to standard composition by some addition of new metal, and every effort is being made to utilize old material to the best advantage and reduce the amount of new metal of all kinds purchased. For a number of years no tin has been used in the lining metal of either passenger or freight car journal-bearings, except such small amounts as come in from re-melting old linings. No change has been made in phosphor bronze used for rod bushings, as we should expect some trouble from bushings pounding out of shape if a phosphor bronze were used which contained less tin or more lead than the present specifications call for. In this, as well as in the case of all other bearing metals, we expect to use our utmost endeavors to economize and to substitute for tin wherever possible. The Tin-plate Industry D. M. Buck,* Pittsburg, Pa.—During the first 5 months of 1918, approximately 11,000,000 Ib. per month of pig tin were consumed in the United States. Solder, bearing metals, bronzes, etc, used about 5,500,000 lb.; collapsible tubes a little more than 250,000 lb.; tin-foil about 500,000 lb.; and the tin- and terne-plate industry somewhat less than 5,000,000 Ib. In an effort to reduce this consumption and thus conserve our tin supplies, several methods of procedure suggest themselves: 1. Salvage. The most careful and systematic collection and re-use of tin and tin-bearing materials is economically important, in that we thus

Jan 1, 1919

By R. V. Mrazek, F. E. Block, S. B. Knapp

The mixed homogeneous and heterogeneous kinetics of the thermal decomposition of tungsten hexacarbonyl were studied by employing a batch reactor. The system was such that a sample of tungsten hexacarbonyl could be injected into the preheated reactor, and the progress of the reaction followed by a simple pressure measurement. Both the homogeneous and heterogeneous reactions were found to be first order, and approximate activation energies were determined for each reaction. It is shown that the dis-proportionation of carbon monoxide to give carbon and carbon dioxide cannot be the source of carbon in tungsten deposits prepared by this reaction. The kinetics of the thermal decomposition of tungsten hexacarbonyl have been investigated as part of a continuing study by the U.S. Bureau of Mines on the decomposition of organometallic compounds. Reactions involving the thermal decomposition of metal carbonyls have a potential application in the preparation of pure metals and fine metal powders. Indeed, it was these applications which provided the impetus for much of the early work involving the carbonyls of nickel1 and iron.&apos; The relative lack of study of other metal carbonyls can be traced to the comparative difficulty in synthesizing these compounds. The most common use for tungsten hexacarbonyl has been as an intermediate in vapor-phase plating.7&apos;8 However, attempts to obtain a carbon-free deposit of tungsten by this method have not been successful, and some investigators have taken advantage of the carbon contamination and used this process to form tungsten carbide deposits.lo Other investigators have studied the thermodynamic properties11"14 and molecular structure of tungsten hexacarbonyl. However, very little is known about the kinetics of this thermal decomposition, the mechanisms involved," or the source of carbon in the resulting plate. In contrast, studies have been made of the kinetics of the thermal decomposition of nickel tetracarbonyl, iron pentacarbonyl, and molybdenum hexacarbonyl.&apos;l It has been found that these thermal decompositions occur by a mechanism which is partially heterogeneous in nature. Information available on the equilibrium constants for the decomposition of tungsten hexacarbonyl was used to determine a temperature range, 500" to 560°K, in which the reaction could be expected to be essentially complete. APPARATUS The apparatus used allowed the injection of a sample of tungsten hexacarbonyl into a preheated batch reactor and the use of a simple pressure measurement to follow the progress of the reaction in the sealed reactor. The pressure was sensed by means of a pressure transducer (Consolidated Electrodynamics Corp., 0.3 pct)* capable of operating at the *Reference to specific products is made to facilitate understanding and does not imply endorsement of such brands by the Bureau of Mines._______ reaction temperature. This type of sensing element was chosen to avoid the problem of condensation of the sublimed carbonyl in the capillary tubing leading to any type of remote pressure-sensing device. stirring was provided by rotating the entire apparatus. Glass beads placed in the reactor provided a pulsating agitation. To minimize thermal gradients in the reactor walls, the reactor was constructed of aluminum. The support tube which held the reactor in the furnace was thin-walled stainless steel to minimize heat conduction out of the reactor. As a result of these measures, a nearly uniform temperature (°C) was maintained throughout the reactor. Fig. 1 is a schematic diagram of the apparatus. The small gear motor rotated the entire apparatus at about 200 rpm. The bearings shown at the ends of the air cylinder were perforated to allow air to be fed to the charging piston and to allow inert gas to be fed to the reactor during the preheating period. The sample was simultaneously injected and sealed inside the reactor by operation of the air piston. Fig. 2 shows a cross section of the air cylinder and the adjoining portion of the support tube leading to the reactor. The sample carrier is shown in place at the right-hand end of the injection rod extending from the air piston. The piston is shown in the retracted position, as it would be prior to the start of an experiment. The small Teflon gasket which encircled the sample carrier at the end of the injection rod sealed the reactor when the sample was injected. This seal was maintained throughout the test by maintaining air pressure on the piston. The sample carrier was a 2-in. section of thin-walled, -in.-diam nickel tubing with an internal blank about 1 in. from the base and with the base end sealed.

Jan 1, 1969