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By John Wulff

IN a previous paper Burwell and Wulff1 have shown by electron diffraction studies that allotropic transformations can be induced in 18-8 stainless steel by polishing to a depth of about 5 X 10-5 cm. The development of a successful etching technique, which removes accountable amounts of metal from the surface without pitting and without changing the root-mean-square profile as measured with an Abbot profilometer, led to the application of the whole technique and material to an investigation of various mechanical methods of surface preparation, such as grinding, lapping, superfinishing and cold-rolling. Ideally suited to such a study is 18-8 of low carbon and nitrogen content. The material can be heat-treated to produce a coarse-grained single-phase structure. On cold deformation there occurs not only a reduction in grain size but, at regions of maximum stress, a change of face-centered material to body-centered material, provided the metal is worked below about 200°C. When worked between 200° and 415°C., diffraction studies evidence a reduction in grain size without the appearance of any new body-centered ferrite. Ferrite, which can be referred also to strains induced by carbide precipitation, is evident when the material is worked at temperatures between 415° and 800°C. Stainless steel is advantageous because the usual surface-finishing operations do not readily oxidize it to any appreciable depth. In order to produce detectable oxide films on the surface of austenitic 18-8 in a time equivalent to that required to produce, for example, a fine ground finish on ½ sq. in., the sample must be held in a furnace or oxygen stream above 600°C. By using longer heating times, it is possible to achieve measurable oxide films on samples whose surface temperatures exceed only about 250°C. EXPERIMENTAL PROCEDURE The apparatus, material, and technique described in the previous paper1 were employed in this investigation. Samples of 18-8, 1 by 1 cm. by 4 mm., were carefully annealed in the austenitic range to produce a coarse-grained structure. They were then quenched and pickled to remove scale. On a lapping machine of the Graton2 type, both sides of each sample were polished to a flatness of 1/6 a wave length of sodium D light. Thereafter they were electrolytically etched to remove at least 1 X 10-3 cm. of the surface, a depth that is well below that of any deformations induced by surface preparation. Samples of this material, carefully mounted in steel holders, were then sent to various industrial organizations known for special finishing techniques. In the instrument shops at the Massachusetts Institute of Technology check samples were finished by the same methods, as far as they were available. Abbot profilometer3 readings were made on all the samples, which were then carefully degreased in double distilled benzine and alcohol, dried in a hot-filtered air blast, and kept in a desiccator. Suc-

Jan 1, 1941

By Raymond E. Byler

THE challenge of unprecedented need for more metals to meet present-day re-armament and domestic requirements is being met with minerals beneficiation projects of great number and variety, and with new and improved methods, techniques, and. equipment. Iron Range Developments Much attention has been given during the year to the tremendous program for beneficiation of taconites and intermediate iron ores which is progressing through large pilot-plant tests preparatory to full-scale production operations. The greatest activity has been directed toward concentration of magnetic taconites on the Mesabi Range. The Reserve Mining Co. has let $75 million in construction contracts for the 2 ½ million-ton-per-yr project (concentrates) at Beaver Bay, Minn., and is building a 300,000-ton-per-yr pilot plant to prove up the magnetic separation and pelletizing operations. Oliver Iron Mining Co. has a pilot plant under construction near Mountain Iron for concentrating magnetic taconites, and is operating experimentally a sintering and nodulizing plant on fine ore screenings and concentrates at Virginia to fully develop agglomeration technique. The Erie Mining Co. plant at Aurora continues its production of concentrates from magnetic taconites which was begun three years ago. No plans have been announced to treat the Mesabi Range nonmagnetic taconites, but F. D. Devaney, Pickands Mather and Co., is studying a new process for magnetically roasting lean ores to make them amenable to low-intensity magnetic concentration. W. R. Van Slyke, Cleveland-Cliffs Iron Co., calls attention to several noteworthy developments in the field of intermediate ores, perhaps the most significant of which has been the first commercial operation of a Dutch State Mines (DSM) cyclone plant at the Buckeye mine of the M. A. Hanna Co. The plant concentrates the +1/4 in. fraction by means of conventional heavy-media treatment after suitable crushing, screening, and washing. The -1/4 in. +65 mesh material is treated in two 12-in. cyclones, the -65 mesh fraction being sent to tailing storage. The plant is operating successfully on feed rates up to 120 tons per hr, and indicates that successful treatment of the fine fractions of Mesabi intermediate ores is imminent. Another commercial-size DSM plant was placed in operation late in the year by Cleveland-Cliffs at the Holman mine, and two additional ones are expected to be in operation next year. Various other methods are also in use at different plants for treatment of the fine fractions, including classification, abrasion milling followed by classification, jigging, and Humphrey spirals. Where it can be economically justified, it seems at present that heavy-media treatment of the -1/4 in. fine fraction will also come into increasing use on the intermediate ores. During 1951 a one-unit, heavy-media plant to treat hematitic crude ore was erected at the Ohio mine on the Marquette Range by Cleveland-Cliffs and plans for another plant at Humboldt to produce 2000 tons of concentrates annually is contemplated, as is also the construction of a plant for agglomera-

Jan 1, 1952

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;''2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.' The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969

ROBERT PEELE, * New York, N. Y.-I should like to ask Mr. Neale how the members of the production committees at the individual mines, who came from the mine workers themselves, were chosen or appointed; also from what classes of employees they usually came? J. B. NEALE.-In the union fields, they were chosen by a local. In the non-union fields, they were chosen either by the men in mass meeting or by the company officials. The last way was very unsatisfactory because it gave the men an opportunity to say that they were going to be passed upon as to whether they were slackers or not, by men chosen by the company. When they were chosen by the locals or at mass meetings of the workers, the appointments have been very much more satisfactory. R. D. HALL, ? New York, N. Y.-The matter of inefficiency on the part of the operator is one that I think we may well take into account, because there is a very large inefficiency on the part of the coal operator; it has arisen from reasons almost beyond his control and will continue for these same reasons. It is no use arguing a moral responsibility on the part of the operator, when you make efficiency very largely a loss to the operator who puts it in force. If you ask a man working on a clay wage to work with more efficiency. he says, "Well, I may do it or I may not," it all depends how he feels, but he does not lose anything financially by not working hard. If you ask the man who is working by the ton to put out more tons, he makes a profit by putting out more tons. How is it with the operator? If he gives a man all the cars he needs and all the power he needs, if he runs after his working men and waits on them, he does not get his coal out any cheaper than before.. He gives the man a better chance and there is more efficiency, but at the same time he has increased his expenses all along the line. At the end of the year he finds that his profits have been less than if he had had less efficiency. The efficiency is really against him in many ways. Because he gets a larger tonnage, he reduces the overhead to a certain extent; but hiss tonnage may not be any greater because he may work fewer days. As Mr. Taylor remarked some tine ago, supposing he puts in a machine that is very much more effective than any he had before, he has the same scale; the miner gets out more coal, but he himself does not get any benefit out of it because he has a scale fixed, so much per ton.

Jan 4, 1919

By D. B. Masson

THE martensitic transformations occurring in ,B AgCd as a result of cold working at room temp.. a-ture and cooling below room ten1erature have been reported by Masson and Barrett.1 These authors found that simple cooling to 127°K caused body-cen-tered-cubic AgCd containing 53.0 at. pct Ag to transform to an orthorhombic structure, while mechanical deformation at room temperature was found to induce a hexagonal structure. Furthermore, they observed that the temperature at which martensite first appeared on cooling, Ms, and that at which the transformation was complete, MI, as well as the corresponding temperatures for the reversion on heating, As and Af, could be ascertained to ± 1°K, although they report these temperatures only for the alloy containing 53.0 at. pct Ag (51.96 wt pct). In the work reported here the temperature range of the transformation on cooling was studied as a function of composition, and further consideration was given to the relationship between the original bcc structure and the transformation-induced hexagonal and orthorhomic structures. EXPERIMENTAL PROCEDURE All samples studied were in the form of annealed 300-mesh powder and were prepared from the constituent metals in the manner described previously.1 The compositions in weight and atomic pct are listed in Columns 1 and 2 of Table I. Method of determination of transformation temperature was the same as utilized previously1—measurement of the intensity of X-rays diffracted by the transformation product. A diagram of the low-temperature sample mount is shown in Fig. 1. This mount was made to fit a GE model XRD-3 X-ray diffraction unit. The powder sample was varnished to a flat surface on a copper sample holder at A. This sample holder was soldered to a brass rod, B, which was in turn soldered to a second copper rod, C. Rod C could be cooled to 78°K by inserting it into a reservoir of liquid nitrogen, D. A heater coil of nichrome wire was wound at E on the sample holder, and by varying the current through the heater a thermal gradient could be maintained along brass rod B. Sample temperatures from 78°K up could be attained and held as long as needed. The sample holder and nitrogen reservoir were insulated by Styrofoam, F, and the sample itself was protected by two radiation shields, G. The X-ray beam entered and left the sample chamber through windoys in the supporting container at H and I. Sample temperatures were measured by a calibrated copper-constantan thermocouple varnished to the sample holder just out of the beam at A. The low-temperature structure had been found to possess orthorhombic symmetry1 and the expected positions of the diffraction maxima were known. Therefore the sample was aligned in the X-ray beam and the Geiger counter of the spectrometer set to receive the most intense orthorhombic reflection without an adjacent interfering cubic reflection. This

Jan 1, 1961

By Pierre I. Desré, Donald T. Hawkins, Ralph Hultgren

The torsion effusion method has been used to measure the vapor pressure of thallium over pure thallium in the temperature range 931" to 996'k The resulting 100 cal per g-atom is in excellent agreement with previous values. Vapor pressures of T1 above seven Ag-Tl alloys ranging from 33 to 90 at. pct T1 were measured at 979K. Calculated silver activities show a positive deviation from Raoult's law, approaching ideality near the liquidus. Measured thallium activities scatter less than previous measurements using the electromotive force technique. Values for the silver component were calculated by Gibbs-Duhem integration. This paper reports the results of a study of the liquid Ag-T1 system by the torsion effusion method. The method has been discussed in detail previously1 and will be only briefly summarized here. The sample is contained in a cell which is suspended on a torsion wire. Vapors effusing from orifices on opposite sides of the cell exert a torque on the wire. The torque is related to the vapor pressure by the following relation: where D is the torsion constant of the wire, 4 the angle of torque, fl and f2 the correction factors determined by Freeman and seamy2 to account for orifice length, a1 and a2 the areas of the orifices, and ql and q2 the distances of the orifices from the axis of rotation. By using the same cell for pure thallium and the alloy, it follows that: so that most systematic errors are eliminated in determining the activities. EXPERIMENTAL 99.999+ pct T1 was obtained from the American Smelting and Refining Co. and 99.999 pct Ag was obtained from Cominco American, Inc. Seven Ag-T1 alloys, ranging in composition from x^\ = 0.33 to 0.90, were prepared by melting together weighed amounts of the pure metals in sealed, evacuated Vycor tubes and quenching the melts in water. The apparatus and graphite cells were the same as those used by Hawkins and Hultgren3 in their study of the Pb-Sn system. RESULTS Ten measurements were made on pure thallium in the temperature range 931" to 996K, and the results are presented in Table I. Values of were calculated using tabulated Gibbs (free) energy functions.4 No dependence of on temperature or orifice size was found, indicating that equilibrium was attained. Data for the Ag-T1 alloys are shown in Table 11. Values were smoothed with respect to composition by a plot of where . DISCUSSION The value = 43,520 * 100 cal per g-atom for pure thallium (95 pct uncertainty limit) is in excellent agreement with previous investigations.4 In the Ag-T1 system, this study shows positive deviations from Raoult's law at all compositions. Fig. l gives the phase diagram according to Hansen, and Fig. 2 presents the activity values measured in this study as well as those from electromotive force measurements at 950°K by Terpilowski, Kundys, and slaby.'

Jan 1, 1969

By R. M. Hays

At the present time, oxidized taconite and semitaconite are not processed on the Mesabi Range except in vely limited tonnages. However, it is estimated that by 1990 shipments from the Range will approach 75 million tons of iron ore per year. To achieve this and future production, either additional magnetic taconite reserves must be proven or oxidized taconite and semitaconite must be processed. One beneficiation process which uses high-intensity magnetic separation and flotation for concentrating oxidized taconite and semitaconite is described. Detailed metallurgical results are given and an economic evaluation of the process is presented with comparison to other processes. The results of the present study indicate that the high-intensity magnetic separation and flotation process appears nearer commercialization for the processing of Mesabi Range semitaconite. The disadvantages of the process are nearer solution and are being solved by well-defined programs. During the twentieth century, the Mesabi Range in northeastern Minnesota has been the main source of iron ore for American steel mills. The Mesabi Range, which is about 120 miles long and up to 3 miles wide, is the pre-glacial outcrop of a group of sedimentary iron-bearing rocks known as the Biwabik formation. The formation, which is 200 to 650 ft thick and dips 50 to 10° to the southeast, is divided into four stratigraphic units. From top to bottom, these are the Upper Slaty, Upper Cherty, Lower Slaty, and Lower Cherty. Since its deposition in Precambrian time, most of the original Biwabik formation has been subject to alteration. Thus, although the iron content of the original formation was quite uniform, major variations in mineral composition now occur both laterally along the length of the formation and vertically within its units. Details of the mineralogical variations in the Biwabik formation have been described by Wolff,' Gruner, 2 and White.3 The unaltered portion of the Biwabik formation includes the magnetite taconites which are being commercially processed by Reserve Mining, Erie Mining, Eveleth Taconite, National Steel, Butler Taconite, and U.S. Steel. These six operations have a capacity of 32 million tons of iron ore pellets per year and have produced approximately 170milion tons of pellets since 1956. Capacity for another 30 million tons of pellets per year is being considered by the industry for the next ten years. This increase will be obtained by constructing new plants and by expanding present operations. Thus, by ! 978, it is estimated that approximately 60 million tons of iron ore vellets will be produced each vear from the magnetite taconites of the Biwabik formation. The portions of the Biwabik formation subjected to intense alteration resulted in direct shipping, wash, and heavy-media ores. Since 1892, 1.8 billion tons of direct shipping ore have been shipped from the Mesabi Range. This ore has been the major source of iron ore for American steel mills. In 1967, about 11 million tons of direct shipping ore and 13 million tons of wash, jig, heavy-media, and other gravity concentrates were shipped from the Mesabi Range.4 These products generally have poorer physical and chemical properties than the iron pellets produced from magnetic taconite. It is predicted that the shipment of these materials will decrease from 24 million tons in 1967 to 6 to 8 million tons in 1975.' This decrease will

Jan 1, 1970

By K. A. Slagle, D. K. Smith

weight obtained. Additives used in conjunction with salt in these slurries have included silica flour, calcium ligno-sulfonate and cellulose retarders, granular lost-circulation materials, bentonite and selected low-water-loss additives that are not significantly deteriorated by the presence of the chloride ion. In some other areas of South Texas, the salt-saturated slurries have been used quite extensively for improvement of the flow properties of slurries and attainment of better circulation characteristics at lower displacement rates. Concurrently with this property, the protection of shales and shaly sands is also realized, as well as useful retardation of the slurry. Resultant superior cementing jobs have been indicated by both communication tests and acoustic logs for bonding to pipe and formation.' In one section of Louisiana, a major oil company has been using salt-saturated API Class A cement with calcium lignosulfonate retarder for cementing through the Miocene at 9,000 to 10,000 ft. This is another of the situations where interbedding of sands and shales exists, creating difficulty in maintaining formation competency when a fresh-water slurry contacts the clay minerals of the formation. Further work has also been done in the shaly Miocene formation at 13,000 to 15,000 ft where fairly close water or gas contacts are encountered. Indications thus far are that better segregation of these various fluids is obtained by use of the saturated salt slurries because of their improved formation bonding characteristics. In addition to the properties of salt in this situation, attainment of turbulent flow at minimum displacement rates has also been accomplished by use of an additive to help provide exceptional dispersion and viscosity reduction of the slurry. Another oil company was encountering considerable expense in completing wells in Southwestern Louisiana due to extensive block squeeze requirements for effective separation of zones. A very effective mud program was being used to minimize washout in the shale sections and, apparently, a nearly gauge-size hole was being obtained. However, primary cementing results with fresh-water slurries were generally poor. On a few occasions when slurry was actually circulated to the surface, large pieces of shale formation were brought out of the hole with the slurry, indicating a severely water-sensitive, sloughing formation. Inhibition of shale heaving was being accomvlished in the drilling program, and immediately indone ipon circulation of the fresh-water slurry even though it contained a low-fluid-loss additive to reduce filtrate damage in the sands. The subsequent change to salt-saturated slurry yielded 11 successful primary cement jobs out of 12, compared to the previous success ratio of practically zero. Since these were deep, high-temperature wells in the range of 13,000 ft with high-pressure zones necessitating 17.5-lb/gal fluid densities, the slurry used was API Class E cement, silica flour, weight material, retarder, salt saturation (which also reduced the amount of weight material) and maintenance of low fluid loss by use of a salt-compatible additive. Other salt slurries have been used to a limited extent in this same general area for similar problems at depths ranging from 5,000 to 17,000 ft. In the shallower wells, the cement has usually been API Class A where the salt functions as a retarder, and in the deeper wells API Class E cement is used with the additional salt advantage being its increased slurry weight and inability to dissolve salt stringers. A considerable number of squeeze jobs have also been done on older wells using the salt-saturated slurries with very good results. MID-CONTINENT In North Texas, salt-water slurries have been used for cementing the Woodbine sand, Strawn sand, KMA sand and Pettit lime. Shales surrounding these formations have created the same difficulty in obtaining separation of producing zones that has been the problem in other areas. Depths in this area range from 3,400 ft for the Strawn to 7,400 ft for the Woodbine, and concentration of salt has varied accordingly. In the deeper wells, where retardation is desired, saturated salt-water cement is used; for the shallower wells, in order to provide shorter waiting-on-cement times, the amount of salt has been 18 per cent by weight of the mixing water. Results have been excellent with no reported failures on any of the salt cement jobs; where acoustic bond logs have indicated indifferent bonds previously, they are indicating very good bonding for the salt slurries. In Oklahoma various shales of Pennsylvanian age exhibit a high degree of sloughing in the presence of fresh water, causing severe washouts above and below sand formations which it is desired to isolate. This situation exists to some degree in practically all parts of Oklahoma and includes formations of other ages such as the Wood-ford shale. For the past few years, salt-saturated cements and displacement rates as high as practical have been used as a remedy for this problem, with very good results. The Layton and Bartlesville formations are two examples of shaly sands where saturated slurries have been helpful. In one area where five wells were drilled through this type of problem shale without obtaining a satisfactory primary cement job, a change was made to salt-saturated cement preceded by a suitable chemical wash for the drilling mud involved. Acoustic bond logging indicated excellent bonding, and final completion bore out this result by being trouble-free. This type of slurry has also been used extensively on squeeze jobs where shales have been heaving around the producing formations. Predominantly, the basic slurry has been either API Class A cement or a pozzolan cement—although, as deeper wells are being drilled, the use of salt in Class E cement is also increasing. Salt cement in West Texas has been used primarily to help prevent channeling through the shales around the Delaware sand, Queens dolomite and Hope lime. Many of the shaly and dirty sands of this area are sensitive to the filtrate from a fresh-water cement. Salt at 16 to 18 per cent by weight of mixing water has been added to centent, and has been effective in controlling formation damage and communication between zones in these formations. Use of these lower salt concentrations is dictated in this area by the relatively low formation temperatures where retardation of the slurry would create unduly long waiting-on-cement times. Also, quite a bit of cementing has been done in this area using salt concentrations in the accelerating range— that is, 2 to 5 per cent by weight of water. Specifically, these concentrations have been used in coiljunction with high percentages of gel to overcome the retarding effect of the calcium lignosulfonate dispersant, although there are probably several shales where these concentrations could provide some degree of formation stability. On several occasions, the salt has also been used to lower the critical velocity or rate for turbulence with the slurry, particularly in the pozzolan cements. On wells in the Hope lime, it has usually been necessary to squeeze the shale above and below the lime to get a water-free completion. Use of salt-saturated slurries has largely eliminated this

By D. H. Forbes, I. B. Cadoff, H. M. Manasevit

Single-crystal silicon films have been obtained on several natural crystal faces of BeO using the thermal decomposition of silane and the hydrogen reduction of silicon tetrachloride. From an analysis of X-ray diffraction data it was determined that the following film-substrate orientation relationships exist: (111) Si 11(0001) BeO, (111) Si 11(1011) BeO, (100) Si 11f1010) BeO. and (110) Si 11(1010) BeO. An analysis of the crystallographic relationships between the film and substrate indicates that a match occurs between the silicon atoms in the film and the berylliuni ion sites in the substrate. This correspondence is in agreement with previous work on the deposition of silicon on sapphire.1-3 silicon on spinel: and tungsten on sapphire. The high resistivity, thermal conductivity, and radiation resistance of beryllium oxide make it an important substrate material for the deposition of thin films of silicon or other semiconductors. The importance of semiconductor-insulator composites to the field of integrated microelectronics has been well-documented in the case of silicon on sapphire.'-' The successful growth of large-area single-crystal silicon on an insulator, sapphire, was first reported in 1963.1,2 Since that time studies have been made of the crystallographic relationships between the deposited film and the sapphire substrate. On the basis of the observed relationships, a model has been proposed relative to the crystallographic requirements for epitaxy between the semiconductor film and the metal oxide substrate.3 It is proposed in this model that epitaxy is the result of a match between atoms of the deposited film and the metal ion sites of the substrate plane. This match is not limited to a 1 to 1 correspondence between sites in the two lattices. Sub- sequent studies of the deposition of silicon on spinel4 and tungsten on sapphire5 have yielded data which support this model. On the basis of this previous work it was felt that silicon on BeO should also fit this model. In the present study, the choice of substrate orientation was limited to the natural faces of synthetic BeO crystals. Of the faces available, the (0001) plane seemed the most favorable for epitaxial growth. EXPERIMENTAL PROCEDURE Silicon films were deposited from silane and silicon tetrachloride in the apparatus shown in Fig. 1. The hydrogen ambient gas was purified by passage either through a DEOXO unit, molecular sieves, and a liquid nitrogen cold trap, or through a heated Pd-Ag thimble. The gas was then mixed with the silicon source materiai and passed over the substrate which lies on a spacer above an inductively heated silicon pedestal. The following deposition conditions were used: a hydrogen flow rate of 3 liters per min with silane and silicon tetrachloride concentrations of 0.2 mole pct and a pedestal temperature of 1175" * 5°C as observed with an optical pyrometer assuming an emissivity of 1.0. Deposition was preceded by a 15- to 30-min hydrogen-etch period conducted at a temperature of 1275°C (obs). Adherent silicon films from 2 to 10 u were grown on the various BeO faces. The substrates were synthetically grown beryllium oxide single crystals ranging from 5 to 10 mm in

Jan 1, 1967

By J. E. 214-000-000-010 Warren, M. R. J. Wyllie, T. Meidav, L. Scharon, R. Uhley, A. J. deWitte

By considering the stoichiometry of the underground combustion process, an equrztion was derived relating the point velocity of the combustion front as a function of the air flux, fuel content, efficiency' of oxygen uitilization, hydrogen:carbon ratio, and ratio of carbon dioxide In carbon monoxide produced. In addition, an equation for cnlcrllating the amount of injected air necessary 10 produce the oil from I Cu. ft of reservoir space was derived. This equation has a direct bearing on evaluating compression costs for the process. Values calculated from these equations are in good agreement with experimentnlly obscrvcd values obtained from laborator) tube runs reported in the literature. The equations are also u\eful for atlcrlyzinf: experinlental data for inconsistencie.r.. I NTRODUCTION The injection of energy in the form of heat into an oil-bearing formation as a means of increasing the recovery of oil has been the subject of much discussion and experimentation as far back as 1920. The ideas have ranged from the injection of steam to the direct use of electricity as a means of getting thermal energy into a formation. However, most laboratory and field studies have been confined to the process whereby a portion of the crude in the reservoir is burned to generate the necessary heat to increase the mobility of the oil by reducing its viscosity. A recent paper by W. L. Martin, et al.', described the results of a number of laboratory experiments in which the combustion process was studied in a sandpack. Studies such as this indicate that with the temperatures involved, the oil is partially coked in this process and it is this coke which provides the fuel for combustion. The combustion of this residual coke can be analyzed theoretically by applying simple stoich-iometric principles to the combustion process. It is the purpose of this paper to compare the results reported in these experiments with those obtained from theoretical considerations. The variables studied by Martin, et al, among others, include combustion front velocity, air flux, oxygen utilization, fuel concentration, ratio of carbon dioxide and carbon monoxide in combustion gases, and the hydrogen:carbon ratio of the residual fuel. All these variables come into consideration when the stoichiometry of the combustion process is studied. The experimental conditions and results are tabulated in Tables 3 and 4 of Ref. 1. For purposes of comparison with calculated results, it was necessary to change the units of a number of the variables. UNDERGROUND COMBUSTION STOICHIOMETRY The combustion or oxidation of the carbonaceous residue or "coke" on the sand can be described in terms of the equation: where n is atomic ratio of hydrogen to carbon, m is ratio of moles of CO2 to CO produced, and CH. is taken as the unit molecular weight, realizing that actually the coke has a large range of high molecular weights. Assuming that all the fuel laid down in the sand is burned, the ratio of moles of oxygen consumed to moles of coke can be written as follows. Moles 0MolesMolescoke In terms of moles O2 per pound of coke, where 12 + n is the molecular weight in pounds per mole. If the 0, consumed is measured in standard cubic feet (60°F and 1 atm) and the coke in pounds per cubic foot of formation, 2, then:

By William E. Galloway, Gary E. Smith, Christopher D. Henry

INTRODUCTION Studies relating to the Oakville aquifer as presented in this report and by Henry et al. (this volume), are part of a larger , comprehensive examination of regional and local stratigraphic, hydro- geologic, and geochemical parameters within the Oakville Formation recently completed by the Bureau of Economic Geology. The Oakville serves both as a major Gulf Coast aquifer and an important uranium host (Fig. 1). Regional and local controls on hydrodynamics and hydrochemistry have important implications for hydrochemical exploration, the establishment of premining baseline parameters, and the design of post mining restoration procedures. Investigations of the Oakville Formation were de- signed for the purpose of determining the response of the aquifer to uranium extraction and were funded by the U.S. Environmental Protection Agency under grant numbers R-805357-01 and R-805357-02. Physical Stratigraphy Physical stratigraphic analysis shows that the Oakville Sandstone, a lithostratigraphic unit deposited by a major coastal-plain f luvial system, consists of five mappable, component depositional elements (Figs. 2 and 3). Each major component element is the product of one or more rivers traversing the Miocene coastal plain. In turn, each river possessed a unique sediment load, discharge characteristics, and source terrane. Consequently, each element exhibits distinguishing geometric and compositional parameters that potentially influence the flux and hydrochemical evolution of contained ground waters (Galloway, Henry, and Smith, in preparation). The Oakvil le Sandstone, as mapped and interpreted as a lithostratigraphic unit in the study area, corresponds closely to the Jasper aquifer system, an equally well-defined Gulf Coastal Plain hydrogeologic unit (Baker, 1978). Principal surrounding hydrogeologic units include the underlying Catahoula confining system, the Jasper aquifer system itself, and the overlying Burkeville confining system (lower Fleming mudstones). The Evangeline aquifer system includes much of the Fleming Formation. The Jasper aquifer system is bounded above and below by relatively less transmissive, finer grained confining systems, although absolute transmissivity varies greatly within both the Jasper and confining units. Lithostratigraphic and hydrogeologic boundaries coincide almost exactly within the Hebbronville flu- vial axis (Fig. 3). Correspondence of geologic and hydrostratigraphic boundaries is good within the George West axis; farther to the northeast the correlation of the Jasper aquifer with units mapped as Oakville Formation diverges to varying degrees. A complete analysis of these trends and a study of the depositional facies comprising the Oakvillle are included in Galloway, Henry, and Smith (in preparation). REGIONAL HYDROGEOLOGY The stratigraphic, compositional, and structural framework of the Oakville Formation and the mosaic of interrelated depositional facies that are combined in this framework play a key role in defining the hydrogeology of the Oakville. Furthermore, a combination of climate and hydrogeology, as well as past and present socioeconomic conditions, has determined water and land use patterns within the region of Oakville outcrop. Utilization of Oakville Ground Water Stratigraphic control for determining which wells produce ground water from the Oakville aquifer was established by preparing structural and isopach maps of the Oakville Formation using regional electric log cross sections. Surface elevation and screened interval data (or total well depth, if open-hole completion techniques were used) from each water well, combined with the stratigraphic data, allowed accurate assessment of the producing aquifer for individual wells. Information on well and screen depths, water levels, and usage of water from

Jan 1, 1980

By W. J. Helfrich, C. L. Sollenberger

Many present direct reduction processes utilize iron ore concentrates for the production of sponge iron and the sponge iron is usually preferred as an agglomerate. Pelletizing a high grade iron oxide concentrate prior to reduction is a simple approach to the high capacity production of a uniform and agglomerated sponge iron product. The present paper describes the effect of different atmospheres and physical characteristics on the reduction of pelletized iron oxide concentrates. The kinetics of iron oxide reduction have been I studied by numerous investigators1-4 and a rate equation for the hydrogen reduction of hematite and magnetite has been proposed. Mc Kewan' obtained kinetic data for the reduction of hematite spheres sintered at 13'70°C (2498'F'). The kinetics of magnetite reduction was studied by Quets. He compacted the oxide at a pressure of 1 ton per sq cm and sintered the specimens to densities of 95 to 96 pct of theoretical. These studies demonstrated that the reduction of iron oxide is a topochemical process and that the rate of reduction is proportional to the receding surface area of remaining iron oxide. Thus, the measurement of the kinetics of iron oxide reduction depends upon the development of a measurable and well defined interface between metal and reacting oxide. It is evident that the reduction rate will be constant only when the rate of formation of the reaction product layer is constant. It was recognized by Joseph' and Edstrom' that the physical character of the oxide will determine the configuration of the interface between oxide and metal. The reduction of oxides which exhibit few pores or no interconnected pores should proceed by topochemical processes. However, if a massive or dense crystalline ore cracks during the reduction of the oxide, thus allowing the reduction to Proceed away from a well defined oxide/metal interface, then the observed reduction rate will vary or change during reduction. From a process standpoint, it would be difficult to apply absolute reduction rates determined for crystalline or nonporous iron oxide to the direct reduction of a porous pellet of iron ore concentrate. Most present direct reduction processes are attempts to utilize iron ore concentraates in the production of sponge iron. The sponge iron is usually preferred in an agglomerated form for subsequent melting practices. Pelletizing a high grade iron oxide concentrate prior to reduction is a simple approach to the high capacity production of a uniform and agglomerated sponge iron product. One process for preparing such a product has already been de-scribed. This paper describes the effect of different atmospheres and physical characteristics on the reduction of pelletized iron oxide concentrates. ORE CONCENTRATES STUDIED A magnetite concentrate from Reserve Mining Co. and a hematite concentrate from U.S. Steel Corp. were used in preparing pellets for these experiments. A head analysis of these concentrates is given in Table I. To compare the reduction rates of pelletized concentrates, it was necessary that each pellet contain equal amounts of oxygen which could be removed by reduction, regardless of the oxidation state, i.e., Fez% or Fe304. Also, because of the difficulty in preparing spherical pellets of uniform size, weight, density, and porosity for experimental purposes, pellets of a cylindrical shape were formed in a press.

Jan 1, 1961

By John R. Keith

Lead and zinc contents of elm, maple, and oak trees and of soils in which the trees grew were determined in samples from the Upper Mississippi Valley mining district, and from an area outside but contiguous to the district. The lead and zinc analyses of plant materials served to differentiate the mineralized and nonminer-alized areas. Stems contained about two times as much lead and about two to five times as much zinc as did leaves taken from the same stems. Lead and zinc analyses of all soil horizons could be used to differentiate between the two areas. Soils at most sample sites in the mineralized district seemed to be more reliable than plants for geochemical prospecting and are a more practical sampling medium. Soil samples from areas with thick loess cover, however, failed to indicate the presence of mineralized bodies whereas tree samples from the same sites contained anomalous amounts of lead and zinc. It is suggested that in areas of thick loess cover, plant samples could be used in prospecting for lead and zinc. The important part that plants play in the cycling of elements through the soil horizons is well-known. The concentration of elements in the upper soil horizons by the action of plants has been called the Goldschmidt enrichment principle.' The fact that plant species vary greatly in their ability to concentrate particular elements in their tissues is also well-known.' Agricultural literature has dealt extensively with relationships of the major nutritive elements in soils and plants3 The extent, however, to which plant actions cycle the minor nutritive and the nonmetabolic elements in the soil has not been adequately investigated. Lead is non-nutritive and toxic to plants, whereas zinc is a micronutrient in low, but toxic in high, concentrations.4 This report presents the results of a biogeochemical study concerned with the amounts of lead and zinc in some plants and soils that occurred both within and adjacent to the Upper Mississippi Valley lead-zinc district. Field work for this study was done in the summers of 1961 and 1962. SAMPLE TARGETS AND CHEMICAL ANALYSES Geologic and physiographic descriptions of' the district have been made by Heyl 5 and several other authors in a series of U.S. Geological Survey (USGS) reports and quadrangle maps.6-I Sedimentary rocks, mostly dolomite, limestone, shale, and sandstone, of Cambrian, Ordovician, and Silurian age predominate in the area. Mineral deposits are of the vein and cavity-fill type; the principal ore minerals are galena and sphalerite. Vegetation of the area was characterized by Curtis1 6 as southern hardwood forest interspersed with patches of oak savanna and prairie. Plant genera typical of the eastern United States Temperate Zone, including ash, cherry, dogwood, elm, hackberry, hickory, maple, oak, and other woody and herbaceous genera, are present. The natural vegetation has been greatly modified by agricultural, logging, and mining operations. The species of the original flora are present, but not in their former relative abundance. Soils of this district belong, for the most part, to the Brunizem and Gray-Brown Podzolic great soil groups. The Brunizems are the soils developed under prairie vegetation.'' The Gray-Brown Podzolics are the soils developed under deciduous forests,18 They are derived from both bedrock and from loess parent materials, and

Jan 1, 1970

By D. T. Peterson, F. A. Schmidt, J. D. Verhoeven

The velocity of mig-ration of these solutes in thorium metal due to a high amperage dc current was measured at several temperatures. All three solutes migrated in the same direction as the electron flow. Diffusion coefficients were combined with the migration velocities to predict the steady-state concentration profile. Electrotransport was shown to be an effective method of removing carbon, oxygen, and nitrogen from thorium and resistance ratios several times larger than for crystal bar thorium were achieved. However, the maxirnum attained purification was well below the predicted values, apparently due to some form of contamination. THE migration of solutes in metals when a high current density dc current is passed has been known for many years. This phenomenon has been the subject of a number of reviews published in recent years.l~* Many of the earlier investigators of electromigration of interstitial solutes interpreted the direction and velocity of migration on the basis of a charge on the solute particle. This interpretation is unclear because, in a given experiment, one cannot separate the contributions to the force moving the solute which arise from the charge on the solute in an electric field gradient and the momentum transfer from the scattering of the electrons or holes. There have been only a few quantitative measurements of interstitial migration velocities and some of these have been characterized by poor accuracy or by errors in the analysis of the experiment. The electrotransport mobilities of carbon, nitrogen, and oxygen in thorium were determined by observing the rate of movement of a discontinuity in the concentration profile. This method was used by Carlson el a~.~ to determine the mobilities of interstitial solutes in yttrium and its advantages are discussed in that paper. The specimen is essentially a pair of semi-infinite, bar-type diffusion couples. The electro-transport velocity was measured by observing the displacement of the mean concentration point in a measured length of time. The diffusion coefficients were calculated by the Grube method from the concentration profile. The transport mobilities and diffusion coefficients can be used to predict the concentration profile in an electrotransport experiment of a given time, current density, and specimen length. At long times a steady state will be reached such that the natural logarithm of the concentration of each solute varies linearly along the bar with a slope which is equal to the velocity of the migrating solute divided by its diffusion coefficient. The estimation of the purification potential of electrotransport is discussed by ~erhoeven.' A comparison of the concentration profile and the purification which should be expected from known solute velocities and diffusion coefficients with that which is obtained in an experiment can be very useful in indicating whether the maximum possible purification has been achieved. EXPERIMENTAL METHOD The apparatus used in this study consisted of a sample chamber which was equipped with two electrodes, a sight glass, and a flange for mounting to a high-vacuum system capable of obtaining pressure of 2 x lo-? Torr. The chamber was made of stainless steel and was 4 in. in diam and 6 in. long. The seal between the electrodes and the chamber was made with "0" rings and compression bushings. The thorium specimens were threaded and screwed into tantalum "U"-shaped adapters attached to the ends of the electrodes. This arrangement is shown in Fig. 1

Jan 1, 1967

By W. R. Kube, W. H. Oppelt

Five low-rank coals, including two lignites, a steam-dried lignite, and two subbituminous coals, were carbonized at 940°F, in a bench-scale carbon-ize~ with a nitrogen and hydrogen atmosphere, or both, using pressures from atmospheric to 1000 psig. Coking characteristics were observed, and yields, composition, and distribution of products from thermal degradation were determined. The influence of pressure on yields from coal carbonization, as well as on modification of coke structure, has long been of interest. One of the first attempts at pressure carbonization was that of Capps and Hulett1 who in 1917 investigated the effects of pressure ranging from 1 to 20 atm on yields at 600° C for bituminous and subbituminous coals. High-pressure carbonization has not been used commercially for coke production. More recently, carbonization at relatively high pressure in the presence of catalysts and hydrogen has been proposed for the production of metallurgical-grade coke from low-rank fuels.' Another approach involves carbonization at high pressure in a hydrogen atmosphere to produce heating gas and a solid residue that is gasified with oxygen and steam to produce the hydrogen required for hydro-genation 3-4 or, alternatively, is burned to raise steam. Recently it has been proposed to carbonize coal under pressure, burn the gas in a gas turbine to produce power, and use the solid residue as fuel in a conventional steam-power plant.5 Our primary interest in pressure carbonization stems from an attempt to determine the influence of pressure on the coking characteristics of lignite to design a high-pressure slagging gasifier using oxygen and steam. At atmospheric pressure, North Dakota lignite is generally considered to be non-coking. However, lignite and subbituminous coals have been reported to show increased agglomeration properties in steam, hydrogen, or carbon-dioxide atmospheres at elevated pressures, although no strong coke was formed at pressures up to 3000 psig.6 If lignite would agglomerate seriously under gasification conditions, proper flow of charge through the gasifier could not be maintained without installing a mechanical stirring device or destroying the caking properties of the coal before gasification. Data on the caking properties of lignite or other gasification fuel, as well as on yields of products under conditions simulating the carbonization process in the pregasification zone, were required in the preliminary design stage of the gasifier. No information was available concerning the influence of pressure and type of atmosphere on North Dakota lignite. To provide this basic data, the U. S. Bureau of Mines investigated the effect of pressure and a hydrogen or nitrogen-rich atmosphere on the yield of products and on coke formation in a bench-scale pressure carbon-izer. SCOPE OF INVESTIGATION Five coals were tested at 940°F in nitrogen and hydrogen atmospheres, at pressures from atmospheric to 1000 psig. Yields and composition of solid, liquid, and gaseous products were determined as a function of the process pressure, and attention was given to the physical appearance of the solid residue. Percentage of carbon converted, sulfur retained in char, and thermal balances were calculated. In this paper, primary consideration is given to carbonization in a nitrogen atmosphere and to data concerning the solid phase. The effect of pressure in hydrogen is presented in detail for only one lignite. More complete information on the response of the other coals in a hydrogen atmosphere will be published in a USBM Report of Investigations. DESCRIPTION OF EQUIPMENT Details of the bench-scale pressure carbonizer are given in Fig. 1. The body of the carbonizer was

Jan 1, 1961

By James E. Lawver, James L. Wright

This paper describes the design of a cell used to measure the electrical conductivity, or the reciprocal resistivity, of granular materials. It also establishes a quantitative relationship between the electrical conductivity and the electrical separation of selected mineral samples. It is estimated' that the free world produces about 13 million tons of mineral concentrates a year by electrostatic or electrodynamic methods. At least 95% of these concentrates are produced by corona discharge type machines that separate minerals by exploiting the differences in their electrical conductivity. But, what is meant by the electrical conductivity of a mineral? How large a difference in the electrical conductivity of two mineral species is necessary to effect a separation? Just what is the role of conductivity in electrical separations with regard to capacity and selectivity? There is a considerable amount of information in the literature on both the mechanisms of conduction and the values of the electrical conductivity of pure single-crystal mineral specimens. In addition, some insight into the role of mineral conductivity can be obtained by referring to a Bureau of Mines publication' in which 95 minerals have been grouped as conductors or insulators as a function of temperature. The classification was made on the basis of the percent of weight that reported as "conductors" in an electrical separator. But, as is often the case in the mineral industry, practical application leads theory — and there is little useful information in the literature giving any kind of quantitative relationship between electrical conductivity and electrical separations. The problem is a bit complex because electrical conductivity per se — which can be rather easily measured on large, single grains — is not sufficiently informative to permit quantitative predictions of the separability of the mineral system. Practical "high-tension"* separations are made at such feed rates that the band of minerals on the rotor is multilayered in thickness. Thus, the effective conductivities of minerals as seen by a high-tension machine include particle-to-particle contact resistance, which is often a controlling factor in making a separation. This is particularly true when the mineral grains are coated with slime or with a dielectric surface film. From a high-tension separation viewpoint, one is actually concerned with the time required for corona-charged grains to lose enough charge so that the centrifugal force acting on the particles exceeds the image force holding the grains to the rotor. This calculation requires a knowledge of the effective mineral conductivity s. (The conductivity of the metal rotor is sufficiently greater than that of the minerals so that it need not be considered in charge decay calculations.) The charge density at time t can be approximated by the relaxation equation.3 where t 5 charge density at time t r, - charge density when t = 0 cr e total electrical conductivity £ = permittivity The time required for the charge density to fall to l/e of its initial value is called the relaxation time and is numerically equal to €/n. AS defined here, u is the conductivity of an element of homogeneous grains making contact with each other and with a grounded rotor. This paper deals with the design of a conductivity cell used to measure a, or its reciprocal p, the electrical resistivity. CELL DESIGN Initial test work was performed with a cell recommended by ASTM.4 Since the reproducibility with the ASTM cell was not satisfactory, it was decided to

Jan 1, 1970

By J. D. Forrester, Erich Sarapuu, T. C. Cheasley

Electrocarbonization of coal will produce cheap fuel for electric power plants. The complete electrification of industry and domestic power consumption of gas generated as fuel in situ is a worthwhile goal for the coal industry. Production of synthetic oils, gasoline, and coal chemicals from coal gas will create additional new markets for the coal industry. RANKING high in the nation's wealth of natural resources, readily available liquid and gaseous hydrocarbons are nevertheless falling steadily in supply, while industrial requirements for hydrocarbon compounds are greater today than during the peak period of World War 11. Theoretically, several processes will increase the future supply of liquid and gaseous fuels, but the practical application of these methods depends on two controlling factors: 1—that enough carbon-bearing material be available to warrant industrial exploitation, and 2—that the given process be physically, chemically, and economically applicable. With regard to the first factor, the Western Hemisphere is fortunately well supplied, see Table I. Table I not only shows the extensive occurrence of many fuel sources, but also the wide discrepancy among quantities of fuel substances in various materials. Great quantities of potentially available fuel have not been recovered. Many coal seams and other hydrocarbon-bearing deposits are so situated that production is uneconomical by present-day mining or oilwell pumping methods, and even in many exploitable deposits where the most efficient production methods are used a large proportion of material is never recovered. Industrial production of hydrocarbon liquids and gases must be better balanced, and processes must be developed which will convert coals, oil sand, and oil shales into fabricated commodities. Among the techniques employed by scientists and engineers to secure fuel masses not economically available at present are several processes of underground gasification. These are all concerned with converting raw materials into gaseous products by thermal treatment of source substances while they are still in the ground and therefore require that a subsurface heat (fire) zone be induced to affect pervasively the buried raw fuel deposit. This is possible only where sufficiently high temperature exists and where the fuel material is satisfactorily opened or channelized. Also, to compete successfully with common mining or oilfield practices, a given method must be controllable and must not involve greater operational expense than regular methods. Preferably, it should be less expensive. Since the close of World War 11, England has continued field studies of underground gasification methods. Experiments have also been conducted in Sweden, Estonia, France, Belgium, Italy, and Germany. The U. S. Government has sponsored field studies at Gorgas, Ala., and because gasification in situ is vitally important to establishment of the nation's fuel resources, the mining engineering department at the Missouri School of Mines has been actively interested in developing the process of underground electrocarbonization. Research was conceived by Erich Sarapuu, and preliminary experiments in treating bituminous coal were begun at the school in September 1947. The work consisted of laboratory experimentation until June 1948, at which time, through a cooperative agreement with the Sinclair Coal Co. of Missouri, pilot plant studies were instituted at the Tiger mine of the Hume-Sinclair Coal Co. near Hume, Mo., to test the encouraging laboratory findings. This comprehensive field program was pursued continuously until the beginning of 1952."'" The broad term underground electrocarbonization describes a unique gasification process that releases by electricity the desired economic constituents from a raw carbon-bearing material, converting the substance of such deposits into deliverable form and greatly reducing the cost-of-mining factor. Underground electrocarbonization is not subject to the major limitations of many other underground gasifi-

Jan 1, 1955

By H. C. Rogers, B. W. Roberts

Vanadium foils and wires, either cold-worked or recrystallized, show a ductile-brittle-ductile fracture sequence with temperature. At about 150°C the hydrogenated vanadium wires are found to be ductile. At room temperature the wires show brittle fracture, and at liquid nitrogen temperature the wires are again ductile, although to a lesser extent than found at 150°C. Hydrogenated cold-rolled vanadium foils have been found to fracture in unusually straight lines along the [100] texture directions. The hydrogen content required to show this [loo] texture fracture is limited to a few atomic percent in range. Hydrogen content above this range causes fracture to occur in random directions. PRELIMINARY experiments with hydrogenated vanadium foils indicated that the embrittling effect of the hydrogen on the vanadium, which was severe at room temperature, was reduced at both lower and higher temperatures. In order to investigate more quantitatively the ductility changes with temperature, vanadium wires were tested in tension at three temperatures. The reduction of area was measured and the fractures examined. Specimen Preparation—The material used was kindly supplied by A. U. Seyboltl in the form of M-in. rod. The nominal analysis was: 99.2 pct V assay, 0.2 pct C, 0.01 pct Si, 0.01 pct Fe, 0.015 pct Ca, 0.02 pct O,, 0.01 pct N2, and 0.003 pct H,. The specimens were 0.035-in. diam wires. These were prepared by cold-swaging the supplied rod to the final diameter without intermediate anneal. They were finished with long-bearing dies. The surface was then given a light polishing with 0 emery paper and degreased in trichlorethylene. An X-ray check indicated that the cold-swaged wire had a fairly strong [110] fiber texture. The wires were then recrystallized in vacuum in continuously pumped quartz tubes at two temperatures to give two different grain sizes. One group of wires was given 45 min at 800°C; another, 60 min at 1000°C. The microstructures in Fig. 1 show the wires after they have been electropolished and elec-troetched in 10 pct HCI. After the 800°C anneal, the vanadium grains had a diameter of 1 to 2p and there appeared to be a tendency to elongation in the longitudinal direction. However, the latter may be an etching effect. After the 1000°C anneal, the grains appeared to be equi-axed, but there was a very large spread in grain size, probably due to some impurity segregation in the wire, Fig. 1, right. The grain diameters varied between the limits of 1 to 150p. The small particles shown particularly clearly in Fig. 1, left, are also visible on the polished surface of all samples before etching and are undoubtedly carbides and nitrides of vanadium. An X-ray check indicated these annealed wires had a strong [110} recrystallization fiber texture. The hydrogenation was carried out in an iron retort with dry hydrogen flowing through it, the retort and contents being heated in a tube furnace with a hydrogen atmosphere. The hydrogenation temperature was approximately 500°C. The hydro-genation times chosen were approximately those which would be just enough to cause the vanadium to be brittle at room temperature and thus allow the greatest chance for ductility to occur at the other two temperatures. Part of the fine grained specimens were hydrogenated for 21/2 min at 490°C. Part of the coarse grained specimens were hydro-genated for 11/2 min at 515°C.

Jan 1, 1957

By W. R. Wilcox

The camphor-anthracene system was chosen as a transparent low-melting analog of the zirconium carbide -graphite system. Camphor and zirconium car -bide both grow nonfaceted, while casting of mixtures yields platelets of both anthracene and graphite. Zone melting of thin layers of organic was observed under the microscope. Irregular lamellar structures were produced at high values of the ratio of the temperature gradient G to the zoning rate V. The anthracene invariably led the camphor, indicating lower kinetic undercooling for the anthracene. The lamellar spacing was an order of magnitude greater than typical spacings for metal eutectic systems. Exact behavior depended on orientation of the anthracene. Oriented dendritic structures were produced at low values of G/V. Transient and oscillatory behavior were also observed—much of it unexpected. A.RC-CAST refractory carbide-graphite mixtures are promising thermal-shock resistant materials. Oriented structures of these materials would be superior to arc-cast materials for many applications. Mollard and Flemings1 and Cline2 have shown that aligned structures can be obtained for a wide range of Pb-Sn alloys. However, these metals both solidify in a nonfaceted manner while graphite yields platelets or flakes. In addition only small diameter samples of Pb-Sn alloys were produced because it was necessary to avoid free convection and to have high temperature gradients. The purpose of the present work was twofold: 1) To observe the solidification of a transparent low-melting analog of carbide-graphite systems and 2) to see if larger diameter samples can be produced. EXPERIMENTAL PROCEDURE When zirconium carbide-graphite mixtures are cast, the resulting structure naturally depends on composition. Carbide-rich mixtures yield metal-like nonfaceted carbide dendrites in a eutectic matrix. Graphite-rich alloys have graphite platelets in a eutectic matrix. Empirically it was found that camphor-anthracene mixtures produce similar structures with camphor being nonfaceted and anthracene forming plates. The organic eutectic melted at 116°C and was composed of 78 wt pet camphor.3 The camphor used was U.S.P. grade from Fisher Scientific Company; the anthracene was 98+ pet fro Aldrich Chemical Co. The impurity content is judged to be on the order of 1 pet. Mixtures ranging from 50 to 88 wt pet camphor were employed for the experiments. All but one of the experiments were performed on the microscope-stage zone melting apparatus described in detail elsewhere.4 The organic mixtures were contained in horizontal cells made of microscope slides or cover glasses. In most of the cells the organic was present as a very thin layer, thus giving almost two-dimensional growth behavior. The cells were moved slowly under a heated wire, which caused a molten zone to move through the solid at rates ranging from 0.01 to 5.4 cm per hr. The temperature gradient was estimated before moving the zone by measuring the distance between the line where all solid was melted (freezing point) and that where solid first began to melt (eutectic temperature). The temperature gradient was found to be 465°C per cm in the thinnest cells used, which were made by pressing together two microscope cover slips in the organic melt and then rapidly withdrawing them. RESULTS The experimental results are described in four parts: simultaneous growth, dendritic growth, irregular growth, and transients and erratic phenomena. Steady state data are summarized in Fig. 1. Except where noted all comments are for the cells containing a thin layer of organic. A) Simultaneous Growth. Simultaneous and roughly parallel growth of anthracene and camphor was obtained over the full range of compositions investi-

Jan 1, 1970

By David W. Wisecarver, James F. Reynolds

INTRODUCTION The Department of Energy is cooperating with Snowmass Coal Company near Carbondale, Colorado to introduce the longwall mining method in moderate to steeply pitching coal seams in the United States. This venture is part of a coal mining research program directed toward development, trial, and analysis of mining technique8 to improve production and recovery in the more difficult mining conditions such as thick, multiple, and steeply pitchly seams found in the Western U.S. The project at Snowmass is the first attempt in the United States to operate a longwall in a steep coal seam. Plans are to mine three adjacent, successively downslope panels in the eight foot thick seam which varies in pitch from 27 to 33 degrees. During this work, researchers and mine engineers are expected to obtain answers to many engineering questions relative to panel design and development, selection of face equipment and beet operating techniques and procedures. They are also committed to obtaining hard data on costs, recovery, production, safety, and behavior of underground mine structure as the three panels are mined. This information is essential to future mine engineering and profitable mining of pitching Western coal reserves. Development of the first trial panel was begun in 1979 and completed in June 1981. The longwall mining equipment was then installed in the starting room and retreat mining begun on August 11, 1981. Project duration is expected to be about five years during which over tm million tons of coal will be produced. TRAINING The longwall mining method is new to Snowmass. For years the mine produced coal by room and pillar methods using conventional techniques to mine upslope rooms and Alpine F6A miners to cut entries and rooms on strike. Miners were experienced in room and - pillar mining from other mines. News of the longwall demonstration was received enthusiastically by Snowmass miners. Employee interest in the project was 100%. However, there was minimal longwall experience on site. In fact, most of the work force had not even seen a longwall. Mine and company management were well aware of the immediate need to develop trained longwall face mining crews and maintenance people qualified to work on longwall equipment and also expertise in longwall planning, equipment selection, power distribution design, ventilation requirements and panel development. The first approach to answer this huge deficiency in longwall mining experience was obviously training. Hence a training program directed toward those mining specifics most urgent to the beginning mining phases was initiated in mid-1980. Classroom lectures and hands on training, using instructors from equipment suppliers and available company longwall expertise, was conducted in longwall subjects to include face mining procedures, panel development, operation of equipment, equipment assembly and maintenance, electrical circuitry and controls, ventilation, move of longwall equipment, and safety procedures. At the same time, responsible engineers and foremen were sent on a tour of European pitching longwalls to see first hand how other mines working under similar seam conditions conducted their operations. Development techniques, types of equipment, methods for transport of men and materials, and ground control techniques were discussed with engineers, foremen and officials at each mine. This look at European longwall mining operations gave Snowmass good insight into the unique problems associated with longwall mining on 30' pitch. Mining considerations such as face conveyor/ support system slippage downslope, panel development, maintenance, safety considerations, manpower requirements, and haulage methods were covered with European experts

Jan 1, 1982