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By L. A. Bromley, A. W. Petersen

The van Arkel-deBoer method for producing ductile titanium by thermal decomposition of Til, vapor and deposition on an electrically heated filament is modified by film boiling Til liquid on a heated filament, resulting in similar titanium deposition on the filament and liberation of gaseous iodine. The deposition rate is higher and the energy requirement smaller than in the van Arkel process. Many problems must be solved before the process is commercially feasible. TITANIUM of 99.9 pct purity, called ductile titanium, has been produced by a modification of the van Arkel-deBoer&apos; method. In the van Arkel-deBoer method, an electrically heated wire is suspended from two electrodes, which are placed in a container holding TiI, vapor at a low&apos; vapor pressure (usually <5 mm Hg). The vapor diffuses to the hot wire, usually maintained at 1100" to 1600°C,&apos; and decomposes according to the reaction liberating gaseous atomic iodine and depositing solid crystalline titanium on the wire. Estimations based on the data of Runnalls and Pidgeon,&apos; indicate that the rate-control ling step is the diffusion of atomic iodine away from the wire. There appears to be nearly thermodynamic equilibrium at the wire with TiI, and iodine as the main gaseous species. TiI, is almost certainly an important gaseous species in the cooler regions.&apos; The liberated iodine diffuses to a heated source of crude titanium and reacts to form more TiI, vapor, which again diffuses to the hot wire and completes the cyclic process. The foregoing process may be modified by suspending the hot wire in liquid TiI,, instead of the vapor, and obtaining film boiling. This type of boiling is characterized by the formation of a continuous film of vapor over the wire surface. Since only vapor contacts the wire sul.face, the temperature of this surface may be raised as high as desirable, within the limit of mechanical strength requirements for the wire. By properly adjusting the input voltage. the temperature of the wire may be maintained above U0C"C; and by evacuating the vessel holding the liquid TiI, and maintaining a suitable condenser temperature, the vapor pressure of TiI, may be held low. Thus, the conditions of operation of the van Arkel-deBoer method may be approximated with film boiling; and hence, it is postulated that ductile titanium may be produced by this method. Preparation of Til, There are many methods available for the preparation of TiI,; that used in this research was prepared by the direct reaction of titanium sponge in controlled amounts with liquid iodine. Although no difficulty was encountered with this reaction, it has since been pointed out that this method is sometimes dangerous and should be used with caution. The resulting TiI, was purified by distillation. First Film Boiling Experiments Apparatus: The apparatus shown in Fig. 1 was used for film boiling TiI, on short wire filaments. The current to the filament was supplied through a bank of three 5 kva transformers connected in parallel. The current was controlled by adjusting the voltage over a 0 to 67.5 v range with a 7 kva variable transformer on the low voltage side of the bank of transformers. The current and voltage were measured by Weston meters. The sealed-in-glass tungsten electrodes were hard-soldered to the filament for the film boiling of TiI,. The bottom part of the reactor, containing TiI,, was wrapped with ni-chrome heating wires to maintain the TiI, in the liquid state. An ice or liquid nitrogen trap, for solidifying I, vapor and any TiI, not condensed, was attached to the low pressure side of the air-cooled condenser. A Megavac vacuum pump was used. Procedure: A 0.010 in. diam tungsten filament was hard-soldered to the tungsten electrodes. TiI, was melted (mp 156°C) and poured into the reactor chamber; the top of the reactor chamber, containing the electrodes, was replaced. Freezing of the TiI, was prevented by controlling the current to the ni-chrome wires wrapped around the reactor with a 1 kva variable transformer. The mechanical vacuum pump was started and the system evacuated to about 2 mm Hg TiI, vapor pressure. The current to the filament was turned on and the impressed voltage slowly increased with the variable transformer. A sudden drop in current at nearly constant im-

Jan 1, 1957

By E. F. Koch, J. L. Walter

oriented crystals of iron and iron with 3, 5, and 6.25 pct Si were rolled to reductions of 10 and 70 to 97 pct at room temperature. Similarly oriented crystals were deformed in tension. Dislocation substructures of the deformed crystals were observed by transmission electron microscopy to determine the effect of silicon on the formation of substructures. Pole figures were obtained to relate orientation changes to substructure. When rolled 10 pct, the iron crystals and the 3 pct Si-Fe crystals formed cells, 1 and 0.2 u in diameter, respecliuely. Cells were absent in the higher-silicon crystals. Extended dislocations and possible stacking faults were observed in the 6.25 pct Si-Fe crystal rolled 10 pct and annealed at 650°C. The stacking-fault energy was estimated to be 20 ergs per sq cm. Rolling to 70 pct resulted in the formation of sub-bands (0.9 µ wide) ill the iron crystals and transition bands (containing 0.2-µ-wide subbands) in the 3 pct Si crystals. No subbands formed in the 5 pct Si-Fe crystal until it was ankzealed. SliP occurred on (112) planes ill tension. The slip traces on the 3 pct Si crystal were wary while those on the 5 pct Si crystal wvere straight. The strain-hardening coefficient for the 5 pct Si crystal was nearly zero. Cells did not form, at least at elongations up to 10 pet. The results suggest that cross slip of iron is restricted by additions of silicon beyond about 3 pct possibly by formation of immobile extended dislocations. IN a previous paper&apos; the authors described the substructures developed in (100)[001]-oriented crystals of 3 pct Si-Fe which were rolled to reductions of 10 to 90 pct at room temperature. At low reductions (10 to 20 pct) cells, approximately 0.2 to 0.3 ja in diameter, were formed. The cell walls consisted mainly of edge dislocations. With increasing reduction (up to 50 pct) the cells were seen to elongate in the rolling direction. In certain regions of the crystal there were significant reorientations which were characterized as rotations about an axis normal to the (100) or rolling plane. These regions were called "transition bands". The regions in which there were no reorientations were called (&apos;deformation bands". At reductions of 60 to 70 pct the elongated cells in the transition bands became sub-bands separated by low-angle tilt boundaries with angles of disorientation of about 2 deg. The elongated cell structure in the deformation band was replaced by a general distribution of dislocations. It was noted that the width of the subbands in the transition bands remained 0.2 to 0.3 µ; i .e., the width of the subbands was the same as the initial cell diameter for reductions up to at least 70 pct. From this, and from considerations of the mechanism of formation of the transition bands,&apos; it was concluded that the subbands evolved directly from the initial cells. In order to check this conclusion, it was decided to examine the relationship between initial cell diameter and width of subbands produced by large rolling reductions. Cell size is known to be dependent upon the temperature of deformation.2,3 However, preliminary experiments with 3 pct Si-Fe crystals indicated that the change in cell size with increasing temperature of deform,ation was not sufficient for the present purpose. On the other hand, cell diameters generally reported for iron deformed at room temperature2&apos;3 range from 1 to 2 p, a factor of 3 to 10 larger than the cells in 3 pct Si-Fe rolled to 10 pct reduction,&apos; indicating the possibility of a marked dependence of substructure (at least in terms of cell size) on the amount of silicon in iron. Thus, the investigation was enlarged to include the study of the effects of varying silicon content on substructure in lightly rolled as well as in heavily rolled crystals of iron and iron with 3, 5, and 6.25 pct Si. The crystals used in this study all had the same orientation, (100)[001], with respect to rolling plane and rolling direction. These were rolled to reductions of from 10 to 97 pct and the substructures determined by electron transmission microscopy in both the rolled state and after annealing. In addition, stress-strain curves were obtained from (100)[001]-oriented crystals of iron and 3 and 5 pct Si-Fe to determine the effect of silicon on tensile properties. The dislocation substructure of the tensile specimens was also determined for Samples pulled to 2 and 10 pct elongation at room temperature for comparison with the substructures produced by rolling. 1) EXPERIMENTAL PROCEDURE Crystals with 3, 5, and 6.25 pct Si were prepared by annealing 0.012-in.-thick sheets of high-purity Si-Fe in purified argon at 1200°C to effect growth

Jan 1, 1965

By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By A. E. Jenkins, L. A. Baker, N. A. Warner

Rates oj decarburization of levilated Fe-C droplets conlaining 5.5 to 0 pct C have been measured at 1660°C. Gas mixtures of 1, 10, and 100 pct 0, with helium diluenl were used at velocities of 12.5 and 62.5 cm per sec. Rates were independent of carbon concentration in the mell and in good agreement with the calculated rule of oxygen diffusion through the gas boundary layer. The effects of flow rale and total pressure are as predicled and the rates are approxitnalely 2.5 times those with CO2 as oxidant. The mass-transfer correlation used incorporaled the efject of natural convection as well as forced conrection. Graphile spheres are shown to oxidize at the same rate as Fe-C droplets under the same experimental codlions. It is concluded that, for high carbon concentrations in the melt, the rate of- decarburizalion is controlled wholly by the rate of gaseous diffusion. Rate measurements with pure CO, are reported for low carbon concentrations where CO bubbles nucleate within the droplet. Under these circumstances the decarburi-zation decreased with carbon concentration and it is proposed that carbon diffusion is significant in conlrolling the decnvburization rate. In an earlier paper1 decarburization rate measurements were reported for levitated Fe-C alloys at 1660°C but with CO2 as the oxidant. The decarburization rate was found to be independent of carbon concentration in the melt but slightly affected by total pressure. The authors were unable to explain the slight pressure effect but in all other respects the results were consistent with control by diffusion in the gas boundary layer. Subsequent work has been directed at finding the reason for the slight pressure effect and whether the kinetics with oxygen as oxidant parallel those with CO2. Recently Ito and Sano2 have shown that with water vapor-argon atmospheres the decarburization rate is gaseous diffusion controlled until an oxide film appears on the surface. In this work the melts were contained in crucibles. MASS TRANSFER IN THE GAS PHASE In the earlier analysis1 only forced-convection mass transfer was considered. Subsequent recognition of the existence of some free-convection mass transfer explained the observed small effect of total pressure on the decarburization rate. Steinberger and Treybal3 and Kinard, Manning, and Manning4 have developed correlations involving the linear addition of the contribution of radial diffusion, free and forced convection. Steinberger and Treybal&apos;s correlation was chosen as the most applicable to the present work since it correlated most of the data available in the literature and handled the low Reynolds number region exceptionally well. The correlation for (Gr&apos;Sc) < 108 is where Nu&apos; is the Nusselt number for mass transfer based upon the total surface of a sphere in an infinite medium, G&apos; is the mean Grashof number for mass transfer defined by Eq. [2], Sc is the Schmidt number (µ/pDAB)f, Re is the sphere Reynolds number (dpu,pf/µf), p is the viscosity of the gas (poise), p is the density of the gas (g cm-3), Dab is the binary diffusivity for the system A-B (sq cm sec-&apos;), dp is the sphere diameter (cm), u is the approach velocity of the gas (cm sec-I), and subscript f denotes the property value is computed at the film temperature Tf defined by Tf = +1/2(To + Tr) where To is the specimen temperature and T, is the approach gas temperature (oK). Natural convection occurs when inhomogeneities exist in gas density. These may be caused by concentration gradients, temperature gradients, or both. In the present work the temperature gradient between the sphere and the bulk gas was very large and in some cases, for example the runs with pure oxygen, the concentration gradient was also appreciable. The Grashof number defined by Mathers, Madden, and piret5 was used since it took account of both temperature and concentration gradients: where Gr&apos; is the Grashof number for mass transfer (p2fgd3|-yA-yA|/µ2f), Gr is the Grashof number for heat transfer (p2f gd3p|To - T,]/µ2fTf), Pr is the Prandtl number (cpµ/k)f, g is the acceleration due to gravity (cm sec-&apos;f, a is the concentration densification coefficient (1/p)(ap/ayA)T, yA is the mole fraction of component A at the gas-metal interface, yA is the mole fraction of component A in the bulk gas stream, cp is the heat capacity of the gas per unit mass at constant pressure (cal g-I OK-&apos;), and k is the thermal conductivity of the gas (cal cm-&apos; sec-1 OK-1). Mathers et al. tested this combined Grashof number

Jan 1, 1968

By D. T. Peterson, T. Carnahan

The diffusion coejTicients of carbon, nitrogen, and oxyget were determined in $ thorium over the tempernilcre range 1440" io 1715°C. The diffusion coyfiicir?zls are given by: D = 0.022 exp (-27,000/RT) jor carbo)~, D = 0,0032 exp(-l7,00Q/RTj for nitrogen, and D = u.0013 expt(-11,UOU/RT) for oxygen. Cavl~orz was found to increase the hardness of thoriunz nearly linearly with concentration over the range 100 to 1000Ppm carbon. ThORIUM has a fcc structure up to 1365°C and a bcc structure from this temperature to its melting point at 1740°C. Diffusion of carbon, oxygen, and nitrogen in bcc thorium was of interest in connection with the purification of thorium by electrotransport.&apos; In addition, it was possible to measure the diffusion of all three of these interstitial solutes in the same bcc metal. Only in niobium, tantalum, vanadium, and a iron have all three interstitial diffusion coefficients been measured in a given bcc metal. Diffusion coefficients have been measured for carbon and oxygen in a thorium by Peterson2, 3 and for nitrogen by Gerds and Mallett.4 Activation energies for diffusion are reported by the above authors to be 38 kcal per mole for carbon, 22.5 kcal per mole for nitrogen, and 49 kcal per mole for oxygen. Values of the diffusion coefficients of carbon and nitrogen in 3 thorium have been reported by Peterson et al.&apos; However, these were secondary results of their investigation of electrotransport phenomena in thorium and it was hoped that the present study could provide more precise data. EXPERIMENTAL PROCEDURE The specimens used in this study were the well-known pair of semi-infinite bar type. The couple was formed by resistance butt welding two 0.54-cm-diam by 3.0-cm-long bars of thorium together under pure helium, the concentration of the solute being greater in one cylinder than that in the other. The finished couple then contained a concentration step at the weld interface and diffusion proceeded only along the axis of the rod. The thorium used in this study was prepared by the magnesium intermediate alloy method.5 The total impurity content was less than 400 ppm. The major impurities were: carbon, 100 ppm: nitrogen, 50 ppm; and oxygen. 85 ppm. The total metallic impurity content was less than 150 ppm. The high solute concentration portions of the diffusion couples were prepared by adding the solute to the high-purity thorium in a non-consumable electrode arc melting procedure. Carbon and nitrogen were added in the form of spectroscopic graphite and nitrogen gas while a Tho2 layer was dissolved by arc melting to add oxygen. High-purity thorium formed the low concentration portions in the carbon and nitrogen couples. The low oxygen portions were obtained by deoxidizing high-purity thorium with calcium for 3 weeks at 1000°C according to a method reported by Peterson.3 The high C-Th contained 400 ppm C, the high N-Th contained 400 ppm N, the high 0-Th contained 220 ppm 0, and the low 0-Th contained 25 ppm O. The high O-Th was brine-quenched from 1500°C to retain most of the oxygen in solution at room temperature. These concentration levels were all below the solubility limits in 0 thorium at 1400°C. A resistance-heated high-vacuum furnace was used to heat the couples. The samples were mounted horizontally on a tantalum support which had small grooves near each end. Spacer rods of thorium, 0.4 cm in diam, were placed in these grooves to prevent contact between the sample and the tantalum support. This arrangement should have prevented contamination of the sample by contact with the support. In further effort to reduce contamination, the oxygen diffusion couples were sealed inside evacuated outgassed tantalum cylinders lined with thorium foil. Thorium rings around each end of the samples acted as spacers in this case. Pressure during diffusion runs was about 10-6 torr after an initial outgassing stage. Temperature measurements were made by sighting on black body holes in the sample support adjacent to the samples with a Leeds and Northrup disappearing-filament optical pyrometer. Temperatures were constant during a diffusion anneal to ±5C. The observed temperatures were corrected for sight glass absorption after each diffusion run. The pyrometer was checked against a calibrated electronic optical pyrometer and a calibrated tungsten strip lamp with the electronic pyrometer being taken as the standard. All temperature readings agreed to within ±3C over the temperature range 1450" to 1690°C. Time corrections due to diffusion during heating and cooling were necessary because of the short diffusion times. The diffusion times ranged from 6 min for the oxygen sample run at 1690°C to 90 min for the carbon sample run at 1500°C. A series of temperature vs time plots were made for heating and cooling of the samples to the various diffusion temperatures. This data was then used in a method according to shewmon6 to determine the time corrections. The corrections amounted to

Jan 1, 1970

By M. M. Fine

Normally the U. S. produces less than 10 pct of its annual manganese requirement. About 95 pct of domestic consumption is used by the steel industry.&apos; The strategic and critical nature of manganese has been recognized by its inclusion in the national stockpile and by intensified research directed toward cataloging and evaluating domestic manganiferous deposits. The USBM has participated in these activities for many years with field and laboratory studies to assess the extent and potential utilization of domestic manganese ores. One area of particular interest is in the vinicity of Batesville, Ark., where deposits have been mined since 1849 for both manganese and ferruginous manganese ores. Production is centered in Independence County, but deposits are also found in Sharp, Izard, and Stone counties in north-central Arkansas. Miser has described the geology and manganese mineralization in some detail.&apos;. * "he rocks of the area are sedimentary, consisting of sandstone, limestone, shale, and chert. The two formations of greatest importance,&apos; Fernvale limestone and Cason shale, are host rocks of the primary manganese mineralization. Through 1955 the district produced some 230,000 long tons of manganese ore (35 pct Mn or more) and 236,000 tons of ferruginous manganese (10 to 35 pct Mn).5 Most of the ore has been mined from deposits of manganese oxides in residual clays resulting from weathering of the two formations noted above. Concentration methods have been primitive, consisting for the most part of washing. hand picking, and jigging. A significant accomplishment in the district in recent years was the USBM recognition and investigation of the huge manganese potential represented by unaltered Fernvale limestone. systematic reconnaissance of manganiferous limestone and other occurrences has been in progress since 1953 to delineate the extent and tonnage of manganiferous materials. Results of that survey have appeared in two recent publications,1-5 which ascribe to the district an inferred reserve of 166 million long dry tons at a grade of 5 to 6 pct Mn. Most of this was mancaniferous limestone with an estimated content of 5 pct Mn. Specifications: Beneficiation was carried out on a group of manganiferous limestones to develop a way to recover commercial-grade concentrate from this extensive resource. The following chemical specifications were established by the GSA for metallurgical manganese ore acceptable for delivery to the national stockpile: Size specifications were not considered, as it was assumed that the concentrates could be pelletized or sintered. Manganiferous Limestones: Of the 11 samples tested to date, six were taken by cutting vertical channels across beds of limestone outcrops. Diamond drilling through overlying barren chert into unex-posed limestone provided four samples, and the last was a churn drill sample. In general, the samples were dlrk, fossiliferous limestone containing small amounts of braunite, hausmannite, rhodochrosite, massive and micaceous iron and manganese silicates, quartz, barite, and glauconite. The braunite and other manganese oxides partly to completely replaced some of the calcite and fossil material. The calcite was generously stained with mangenese and iron oxides. Phosphorus was present in all samples as collophanite grains, calcium phosphate fossil replacements. or an unidentified manganese-bearing carbonate. The difficulty in separating this complex array of minerals was further complicated by a very intimate association. Although some manganese grains as large as Ik in. were noted, grinding to subsieve sizes would have been necessary to liberate the components. Figs. 1 and 2 are micrographs, at X100, of typical polished sections in which white areas are manganese. gray is gangue, and black areas are surface depressions. By comparison with the 100 mesh opening, it is seen that some of the grains are coarse enough to respond, perhaps to tabling or flotation, but many are obviously beyond the scope of ohysical processing. Partial chemical analyses of the eight samples that were ultimately amenable to concentration are presented in Table 1. BENEFlClATlON RESEARCH Tabling: To take advantage of the presence of sand-size grains, both jigging and tabling were considered at the outset. Jigging was largely ineffective, but tabling achieved a partial recovery from most samples. As an example, the surface material from Baxter Hill was crushed to —28 mesh, hydraulically classified, and the coarsest spigot fraction was tabled to yield a concentrate, middling. and tailing. The latter two were reground to pass 48 mesh, combined with the primary fines, re-classified, and retabled. The middling and tailing were again ground, this time to pass 150 mesh, and deslimed at 20µ in a 3-in. hydraulic cyclone. The cyclone underflow was returned to the table to reclaim a small amount of high-grade manganese. An interesting facet of the gravity concentration developed on certain samples in which braunite was the principal manganese constituent. Since braunite has a Mohs hardness of 6 to 6.5, while the host rock, limestone. is only 3, a differential size reduction took place during crushing, and the

Jan 1, 1960

By Wm. R. Dotson

Forty years ago the atom was split and the Age of Fission dawned. Uranium was the element used in this earth-shaking accomplishment. Thitherto almost unknown to the man in the street, uranium soon became widely and persistently sought. And the quest for this unique material is not likely to diminish during this century. To find is one thing; to own is another. Who owns uranium in the ground? Where no mineral rights in the land have been severed by devise, grant, reservation or lease, the uranium belongs to the fee simple owner of the land. But where there has been a conveyance or reservation of all or part of the "minerals", determining WHAT a substance is has been the traditional way of determining WHO owns it. What, then, is this element called uranium? The 1907 edition of Watts Dictionary of Chemistry calls it "a lustrous, hard, silver-white metal". Of nature&apos;s three prime divisions it falls within the embrace of the mineral kingdom - substances neither animal nor vegetable. In its natural state uranium always is combined with other elements or substances in the form of an ore mineral. May we, then, put to rest any doubt or question as to the nature of uranium and classify it for all purposes, including that of ownership, as mineral? Not quite! That self-same logic would find oil and gas primly ensconced in the animal or vegetable kingdom. Technically, oil and gas are not minerals but legally they have been classified as such. Why? The Supreme Court of Tennessee sought the answer in 1897 in the case of Murray v. Allard, 43 S.W. 355. After citing authorities pro and con, and while admitting their origin to be "decomposition of marine or vegetable organises" that court firmly concluded that since they were obtained by a form of mining, oil and gas were minerals. From the above example two elementary truths emerge. First, for purposes of ownership, uranium is and will be whatever the courts say it is. Secondly, the courts historically and currently favor a practical rather than technical test to determine the "mineral" character of a substance. So now we turn to the jurisprudence for enlightenment and definition. EARLY CASES ALLOT URANIUM TO MINERAL OWNERS Two early cases involving the ownership of uranium followed what had been well-settled mineral within the meaning of the conveyances involved, confirming ownership in the mineral owners. In 1956 the U. S. District Court for New Mexico in the case of New Mexico and Arizona Land Company v. Elkins, 137 F. Supp. 767, appeal dism&apos;d 239 F.2d 645 (10th Cir. 1956), found that a 1946 deed reservation of "all oil, gas and minerals underlying or appurtenant to said lands" included uranium and thorium. The court reasoned that uranium and thorium, being minerals within the scientific, geological and practical meaning of the term, would certainly constitute minerals within the purview of the reservation. While agreeing that uranium and thorium were "minerals", defendants argued that at the tine of execution of the conveyance it could not have been the intention of the parties to reserve them because they had no commercial value in the locality and were, in fact, not known to there exist until their later discovery in 1950. The court re¬jected, as a matter of law, this "lack of knowledge" theory citing the Supreme Court of Kentucky holding in Maynard v. McHenry, 113 S.W. 2d 13, that: "The mere fact that a particular mineral has not been discovered in the vicinity of the land conveyed or is unknown at the time the deed is executed rules of construction and held that uranium was a does not alter the rule . . ." that a grant or exception of "mineral" in a deed includes all mineral substances which can be taken from the land unless restrictive language is used indicating that the parties contemplated something less general than all substances legally cognizable as minerals. Further, argued the defendants, the only feasible mining procedure for such substances was open pit or strip mining, which would destroy the value of the land for grazing or agriculture. Finding that the language of the reservation was clear and unambiguous, the court would not permit the admission of extrinsic evidence as to mining procedures required. Elkins is the first uranium case construing the granting clause involved. In 1958 the Texas Court of Civil Appeals at San Antonio, in Cain v. Neuman, 316 S.W. 2d 915, no writ, held that a 1918 lease conveying "all of the oil, gas, coal and other minerals in and under" the land involved covered uranium. The lease provided a royalty of 1/10th on "other minerals." "We find no Texas precedent which discusses uranium," said the court, "but the usual arguments that uranium is not embraced within a lease are that the ejusden generis rule excludes uranium from the meaning of the lease

Jan 1, 1979

By R. E. Powers, E. H. Kinelski, H. A. Morrissey

A group of 17 American blast-furnace sinters, an American open-hearth sinter, an American iron ore, and a Swedish sinter were used to evaluate testing methods adapted to appraise sinter properties. Statistical calculations were performed on the data to determine correlation coefficients for several sets of sinter properties. Properties of strength and dusting were related to total porosity, slag ratio, and total slag. Reducibility was related to the degree of oxidation of the sinters. THIS report to the American iron and steel industry marks the completion of a 1949 survey of blast-furnace sinter practice sponsored by the Subcommittee on Agglomeration of Fines of the American Iron & Steel Institute. The use of sinter in blast furnaces, sinter properties, raw materials, and sinter plant operation have been reported recently.1,2 After preliminary research and study," test procedures were adapted to appraise the physical and chemical properties of sinter to determine what constitutes a good sinter. During the 1949 to 1950 plant survey each plant submitted a 400-lb grab sample to research personnel at Mellon Institute, Pittsburgh, Pa. A 400-lb sample was also submitted from Sweden. In addition, 2 tons of group 3 fines iron ore were obtained from a Pittsburgh steel plant. The following tests were performed on the iron ore sample and on the 19 sinter samples: chemical analysis; impact test for strength and dusting; reducibility test; surface area measurements, B.E.T. nitrogen adsorption method; S.K. porosity test; Davis tube magnetic analysis; X-ray diffraction analysis for magnetite and hematite; and microstructure. Results of these evaluations are discussed in this paper and supply a critical look at testing procedures used to determine sinter quality. Sinter Tests and Results Each 400-lb grab sample of sinter was secured at a time when it was believed to represent normal production practice at each plant. It was not possible to use the same sampling procedures throughout the survey; consequently samples were taken from blast-furnace bins, cooling tables, and railroad cars. These were very useful for evaluation of test methods, since they were obtained from plants with widely divergent operations. With the exception of Swedish sinter and sinter sample N, which were produced on the Greenawalt type of pans, all survey sinters were produced on the Dwight-Lloyd type of sintering machines. Sinters submitted for test were prepared in identical manner by crushing in a roll crusher (set at 1 in.), mixing, and quartering. To secure specific size fractions for tests, one quarter of the sample was crushed in a jaw crusher and hammer mill to obtain a —10 mesh size. The remainder was screened to obtain specific size fractions. The group 3 fines iron ore was dried and screened and samples were taken from selected screen sizes to be used for various tests. Prior to testing, each ore sample except the —100 mesh fraction was washed with water to remove all fine material and was then dried. This iron ore, a hematitic ore from the Lake Superior region, was used as a base line for comparing results of tests on sinters. The iron ore did not lend itself to impact testing, since it was compacted rather than crushed in the test, and no impact tests are reported. However, the iron ore was subjected to all remaining physical tests to be described. Chemical Analysis: Table I presents chemical analyses performed on the survey sinter samples. Included in this table are data obtained from determination of FeO and the slag relationships: CaO + MgO and total slag (CaO + MgO + SiO, SiO2 + Al2o3 + TiO2). The percentage of FeO was used as an indication of the percentage of magnetite in the sinter. It was believed that slag relationships could be correlated with sinter properties. During initial determination of FeO great disagreement arose among various laboratories, both as to the results and the methods of determining values. Table I lists the values of FeO resulting from the U. S. Steel Corp. method of chemical analysis,&apos; which reports the total FeO soluble in hydrochloric and hydrofluoric acids (metallic iron not removed) with dry ice used to produce the protective atmosphere during digestion. Use of dry ice was a modification required to obtain reproducible results. In this method, the iron silicates and metallic iron are believed to go into solution and are therefore reported as FeO. This is important, for in the study of the microstructure of sinters, glassy constituents suspected of containing FeO as well as crystallized phases of undetermined identity which may also contain FeO have been observed. Strength Test by Impact: In evaluating sinter quality, one of the properties stressed most by blastfurnace operators is strength. This strength may be described as the resistance to breakage during handling of sinter between the sinter plant and the blast-furnace bins. It is also the strength necessary to withstand the burden in the blast-furnace. After

Jan 1, 1955

By N. M. Levine

WHETHER the United States and its allies can W meet the challenge of a war brought by the Communists will depend largely on who wins the battle of steel production. At the present stage of the world situation, the United States and the other members of the Western family of nations have the lead on iron curtain countries. But we have no sure way of knowing what is happening at Magnetogorsk and other Russian iron and steel producing centers. We must also face the possibility that we may have to meet the challenge alone. The fortunes of war and world politics can strip us of friends and co-fighters quickly. The destruction of Hiroshima and Nagasaki are indicative of what the world can expect if war-madness ever grasps the earth again. Our domestic supply of high grade open-pit and underground iron ore is dwindling because of the drain of three wars and higher than ever civilian consumption. The production of iron ore and its eventual use in blast furnaces are the critical problems of an armed democracy today. The world crisis has led to efforts towards beneficiation for increasing ore supplies. The huge reserves represented by the magnetic taconites at the eastern end of the Mesabi, once in production, should provide us with a substantial portion of our native ore for many years. The estimated 10 to 20 million tons of concentrates annually can be increased in an emergency. If we had a certainty of peace for the next 50 to 100 years, the situation would be a stable, hopeful one, aided by importations of high grade ore from sources such as Canada and Venezuela. The hard truth is that we have little surety of peace tomorrow morning. Let us assume &apos;the U. S. could build sufficient processing plants for increasing production of magnetic taconites under the pressure of national emergency. We must also recognize the power of atomic warfare to contaminate an area as large as the Eastern Mesabi. Thus, it becomes imperative to seek some means of protecting our ability to produce the steel we may one day need to survive. The nonmagnetic taconites, completely dwarfing the magnetic taconites areawise as well as tonnage-wise, might provide us with this insurance. Present indications are that they will be considerably more expensive to treat, but in a desperate situation we might be very grateful for ores yielding 40 to 50 pct Fe recoveries at grades of 53 to 58 pct Fe carrying low phosphorus. The University of Wisconsin, because of the difficult iron ore situation in the state, has been working on the nonmagnetic taconite problem for the past three years in the hope of making a contribution toward its eventual solution. In Wisconsin, the Western Gogebic Range has been the state&apos;s most effective iron producing area. Today however, only two mines are in operation, both underground and approaching depths of more than 3000 ft. The range, however, does have a large supply of nonmagnetic taconites and presents a promising field for study. While the Gogebic offers one large source of nonmagnetic taconites, Michigan and Minnesota have even greater supplies of such material. Alabama, the northeastern states and the West all have low grade iron ore sources which might be utilized under extreme conditions. The Gogebic Range located in northeastern Wisconsin and northwestern Michigan has a total length of about 70 miles, about 45 of which are in Wisconsin. The iron formation averages 500 to 600 ft in width, dips 70&apos; to the north and strikes at approximately N 63° E. The formation is sedimentary and consists of six distinct members characterized by alternating divisions of ferruginous chert and ferruginous slate. The footwall is generally quartzitic and the hanging wall of a sideritic slatey character. The iron minerals are mainly hematites with some magnetites, goethites, limonites and small amounts of siderite. In the area studied, very small amounts of iron silicates were observed. The magnetites occurred mostly in the Anvil-Pabst and Pence members, mixed with hematites and representing roughly about 10 to 20 pct of the total iron in the formation, thereby characterizing it as nonmagnetic. The gangue is of various forms of silica such as chert, opal and flint. Complete liberation of iron and gangue minerals is rare. There is always some iron present in the chert ranging from jasper-like solutions to fairly coarse iron oxide specks. Likewise, one always finds finely dispersed silica within the iron minerals. In late 1943 the Bureau of Mines carried out a trenching and sampling program in the two mile stretch between Iron Belt and Pence in Iron County, Wis. Preliminary work was based on samples from one of the four trenches cut by the Bureau of Mines. More detailed work following the preliminary analysis was then undertaken on samples composited from all the trenches, thereby giving a wider and more representative coverage of the area. A study of the

Jan 1, 1952

By John C. Bilello

The brittle fracture behavior of cold-worked sintered tungsten was studied over the temperature range 4.2° to 298°K using a high-sensitivity strain measuring system and electronfractography. Similar observations were made on a swaged electron beam zone-refined monocrystal. In sintered tungsten irreversible plastic deformation was observed during cyclic load-unload tests at stress levels well below the fracture stress for all temperatures, but general microyielding could be detected only down to 202°K. For the zone-refined samples macroyielding occurred at all test temperatures with evidence for twinning below -202°K. The fracture stress of the sintered tmgsten was virtually independent of temperature, while the zone-refined crystal showed a 2.3 times increase over the same temperature range. Electronfractography confirmed the presence of numerous rod-shaped and spherical submicroscopic voids which ranged in diameter from 1400 to 4300A in the sintered tungsten; no voids could be found in the zone-refined tungsten. Contrast effects observed on the replicas in the vicinity of certain voids indicated that plastic deformation could be induced by the local stress concentration. It has been suggested that the presence of these voids may be responsible for the low-temperature brittle failure of sintered tungsten. Based m this suggestim und on the evidence obtained here, a dislocatim model is presented to account for the brittle behavior of sintered tungsten. In this model slip, which is induced by the local high stress concentration in the region at the edge of a favorably oriented void, could cause the void to grow to a microcrack of critical size. STUDIES of brittle fracture in bcc metals have led to the well-known experimental relationships between grain size, yield stress, fracture stress, and temperature which have formed the basis for the various dislocation pile-up1-3 or interaction4&apos;= models for slip-induced microcrack nucleation. While microcracks can be nucleated by deformation twins,6,7 there has been no direct evidence furnished by transmission electron microscopy to support conclusively either the Zener pile-up or Cottrell dislocation reaction models for producing micro-cracks in all "brittle" materials. In addition to the "inverse" grain size relationship for yield and fracture stresses the cottrel14 theory predicts that the fracture stress below the transition temperature should behave in a fashion similar to that of the yield stress above this temperature. Such behavior has been verified for several bcc metals.8-10 With reference to both grain size effects and the tem- perature dependence of the fracture stress below the transition temperature, the behavior of sintered tungsten appears anomalous. Early work by Bechtold and Shewrnon 11 showed no apparent temperature dependence of the fracture stress below the ductile-brittle transition temperature (DBTT). They attributed this result to the intergranular nature of the fractures observed. More recent work by Wronski and Four-deux12&apos;13 on considerably purer material did not show any systematic relationship between the fracture stress and temperature below DBTT. The dependence of flow and fracture stresses on grain size is also not clearly established for sintered tungsten. Koo, for example, has shown that the DBTT for sintered tungsten depended chiefly on the annealing temperature and was relatively insensitive to the actual grain size achieved. Using electrofractography and transmission electron microscopy, Wronski and Fourdeuxl3 showed that numerous spherical and rod-shaped submicroscopic voids could be found in sintered tungsten but not in melted tungsten of nominally the same purity. They suggested that these voids could be responsible for the temperature insensitivity of the fracture stress below the DBTT. In the present work the temperature dependence of the fracture stress for high-purity commercially sintered tungsten has been determined. The presence of submicroscopic voids in sintered materials was confirmed, and these were studied in detail to examine the role they could play in nucleating brittle fracture. A dislocation model is suggested which could cause an inherent spherical void to lengthen into a Griffith crack of critical size. EXPERIMENTAL PROCEDURE Commercially sintered tungsten rod was obtained in the as-swaged condition from Sylvania. A zone-refined crystal was obtained from the same source. This crystal was grown by giving three zone passes (at 25.4 cm per hr) to a sintered rod of high-purity tungsten. The rod axis prior to cold working was -15 deg from the [110] direction. Originally the zone-refined rod was -6 mm in diam; it was reduced to -3 mm by eight swaging passes, at high temperatures, with each step having about the same reduction of area. The final swaging step gave a 7.5 pct reduction of area at 1050°C. All swaging operations were performed in a hydrogen atmosphere. For the sintered rod a similar working schedule was employed. Metal-lographic examination of the sintered material revealed that the cold-worked structure had an apparent grain diameter of -25 u transverse to the swaging direction (obtained by the intercept method). In the longitudinal direction cold-worked grains were approximately 1.5 to 2 times their diameter. No distinct fiber structure could be observed optically for the zone-refined rod. The cold-worked structure in the

Jan 1, 1969

By E. Amott

A test is described in which the wellubility of porous rock is measured as a function of the displacement properties of the rock-water-oil system. Four displacemet operations are carried out: (I) sponlaneous displaceti?ent of water by oil, (2) forced displacement of water by oil oil in the same system using a centrifuging procetllrre, (3) spontaneous displacement of oil by water. and (4) forced displacment of oil by water. Ratios of the spontaneous displacement volumes to the total displucenlent volumes are used as wettability indicates. Cores having clean mineral surfaces (strongly preferentially water-wet) show displacement-by-waler ratios approaching 1.00 and displacement-by-oil ratios of zero. Cores which ([re. strongly preferentinlly oil-wet give the reverse resu1ts. Neutral wellability cores show zero values for both ratios Fresh cores from different oil reservoirs have shown wettabiltties in tlris te.st covering rrlti~ost 111e conlplrtt, range of thr: te.st. Notvever, nlo.s/ of tlle fresh California cores tested were slightly prcfere111icrlly wclter-\vet. The chrrnge.~ in coro u (&apos;liabilities, as indicated hy this te.st, r~.sril/ing from various CO~P hanrlling procedures tt,ere oh.served. In sonie ca.sc,s /Ire ~,cttahilitio.c. of fresh cores were changell by drxi:~g or 11y e.x/rclct ing with iolcreiii~ or. dioxunc~; in o/h~r cases they were 1101 changed. Co~ltrrc/ of cort,.s ~.ith filtrc~t~c. from water-base rlrilling rilrrrls crlrc.sed littlc change in we/ /ahility ivhile contnct with filtrates frorii oil-hus~ ri1rlcl.s tlecrrascrl the prefcrerlcc, of the, cores for )I.NI Usitig thi,s test to ri.crl~lute n~r~ttubili~y, N .vt~ldy was iilarle of /lie correlmtio~i of wettability with wa/erfloocl nil recovery for orttcrop Ohio sand.stone and for Al~ln-tlunl. Resul/.v indicate thml no single correlatioti between these factors applies to different porous rock syste~n. It is thought that diflerences in pore gen~netry resrrlt in diflrrerrce.~ in this correlurio~z. INTRODUCTTON Most investigators who have reported on the wettahility of porous rock have described such rock as prcferentially water-wet or preferentially oil-wet. In some cases a third classification, neutral wettability. has been used. The efficiency of water floods in each of these wettability groups has been described in numerous publications. Several methods for characterizing porous rock wet tability more precisely have been reported,&apos; " but it appears that because of one weakness or another. none of these has been generally accepted. Early in our studies in this field, it was found that the displacement efficiency of oil by water in a particular porous rock having a strong preference for water was quite different from that in a similar rock having only a moderate preference for water. Thus, there appeared to be a need for a practical, reasonably precise wet tability test. one which could classify porous rocks into 10 to 20 different groups rather than the two or three broad groups listed above. The test developed to meet this need is described in this paper. Also, changes in wettability, as indicated hy this test, resulting from various core handling procedures are discussed. Finally, data showing the corrclation of wettability with waterflood oil recovery for two different types of cores are presented and discussed. Some confusion has resulted from the failure of certain writers to define clearly some of the wettability terms they have used. Accordingly, the following commcnts concerning definitions are offered. The wc t ta-hility of a solid surface is the relative preference of that surface to be covered by one of the fluids under consideration. It is felt that this is the generally accepted definition. The fluids being considered must bc specified (or understood) before the term wettability has any significance. In the work reported here these fluids are water (3 per cent brine) and oil (kerosene). The term preferential wettability is sometimes used, but we think that the word preferential is redundant here and should not be used. Tn line with the definitions of Jennings&apos;, a preferentially oil-wet solid surface is regarded as a surface which will show an oil advancing contact angle less than 90" (measured through the oil) in the water-oil-solid system. Oil will spontaneously displace water, if both are at the same pressure, from such a surface. A preferentially water-wet surface is analogous. This is consistent with the wettability definition above. As Jennings has said, frequently the term oil-wet is used to mean the same thing as preferentially oil-wet. However, oil-wet also has been used occasionally referring to an oil-covered surface when the availability of water was limited. To avoid confusion from this source, we do not use the terms oil-wet and water-wet. DESCRIPTION OF WETTABTLITY TEST The following points were considered desirable in a wettability test for our purpose. 1. The test should be a displacement test resembling

By James H. Courtright, Kenyon Richard

TOQUEPALA is a porphyry copper deposit in which mineralization is localized by a large breccia pipe formed in close genetic relation to intrusive rocks. The deposit is in southern Peru, 55 airline miles north of the small city of Tacna and the same distance inland from the port of 110. Quellaveco and Cuajone, geologically similar deposits, lie 12 and 19 miles north of Toquepala. Chuquicamata is 400 miles to the south. The deposit is high on the southwestern slope about 20 miles from the crest of the Cordillera Occidental of the Andes Chain. It lies in a mountainous desert where the steep southwesterly slope of the Andes is dissected by a succession of rapidly downcutting, deep canyons. Local topography is moderately rugged with a dendritic drainage pattern and an elevation of 8000 to 14,000 ft. Volcanic peaks along the crest of the Cordillera rise over 19,000 ft. Local precipitation, including a little snow, amounts to about 10 in. during January and February, but general runoff in the region is slight. Throughout southern Peru the springs and streams are widely separated. Crude canals irrigate small farms on terraced slopes along the streams and provide sparse subsistence to the semi-nomadic inhabitants. During the past decade, engineering and geological explorations of the region, as well as the mineral deposits themselves, have required construction of a network of several hundred miles of roads. Before this, roads extended only a few miles inland. Many areas still can be reached only by trail. Toquepala was briefly described in 19th century geographical literature as a copper deposit, and it received desultory attention from Chilean prospectors early in the present century. It was first recognized as a mineralized zone of possible real importance by geologist O.C. Schmedeman during an exploration trip for Cerro de Paso Copper Corp. in 1937. The discovery was late as compared to earlier recognition of Chuquicamata, Potrerillos, and Braden of Chile and Cerro Verde of southern Peru. This was due partly to the region&apos;s difficult accessibility but principally to the obscure character of the outcrop evidence of copper. From 1938 until 1942 Cerro de Pasco Copper Corp. partially explored the deposit by adits and diamond drillholes. This campaign was supplied by a 60-mule pack train continuously shuttling over a 30-mile trail. Northern Peru Mining & Smelting Co., a wholly owned subsidiary of American Smelting & Refining Co., undertook regional engineering stud- ies in 1945 and drill exploration in 1949. According to published data1 the deposit contains 400 million tons of open pit ore averaging a little over 1 pct Cu. It is currently undergoing large-scale development by Southern Peru Copper Corp., which is owned by American Smelting & Refining, Phelps Dodge, Cerro de Pasco, and Newmont Mining. Summary of Geology: The deposit is situated in a terrane composed of Mesozoic(?) and Tertiary volcanic rocks intruded by dioritic apophyses of the Andean Batholith. These formations are exposed in a northwesterly trending belt about 15 miles wide. Along the northeast they are unconformably overlain by Plio-Pleistocene pyroclastic rocks, which occupy much of the crest of the Andes, and along the southwest they are covered by the Moquegua formation of Pliocene(?) age. The mineralized area, oblong in shape and about 2 miles long, has been a locus of intense igneous activity. Several small intrusive bodies having irregular forms occur within and adjacent to a centrally located, large breccia pipe. The mushroom-shaped orebody consists of a flat-lying enriched zone of predominant chalcocite with a stem-like extension of hypogene chalcopyrite ore in depth within and around the pipe. This breccia pipe is relatively large and has been formed by repeated episodes of brecciation. Small satellitic pipes occur at random within a 2-mile radius of this central pipe. These too were individual sourceways of mineralization, although not always of ore grade. Within and around the zone of breccia pipes and mineralization there are a few faults and veins, but these are discontinuous random structures of minor significance. There are no regional or local systems of faults or other planar structures recognized which could account either for the mechanical development of the breccia pipes or for their localization as a group or as individuals. Hydrothermal alteration is pervasive in the zone of mineralization. Clay minerals appear to be abundant in places, but their percentages are undetermined. Quartz and sericite are the principal alteration products, and in many instances original rock textures are obliterated. The principal sulfides, hypogene pyrite and chalcopyrite and supergene chalcocite, occur mainly as vug fillings in the breccia and as small discrete grains scattered through all the altered rocks. Sulfide veinlets are relatively scarce. Sulfides are more abundant and alteration is more intense in certain rock units, such as the diorite and most of the breccias. Although the Toquepala mineral deposit is similar in most respects to the porphyry copper deposits of southwestern U. S., it most closely resembles the Braden deposit of Chile, as described by Lindgren

Jan 1, 1959

By C. B. Manula, R. Venkataramani

Application of computers to present-day open-pit mining with bucket wheel excavators (BWE) is discussed. The development of the wheel excavators and their use in mining are discussed along with the necessity for building a computer model of the bucket wheel and the mathematical formulation of the problem. The simulation procedure, testing the model, and test results are summarized. Even though the mining industry in 1966 produced more ore than ever before, current extraction rates are only a fraction of what is expected in the later years of the 20th century. Nearly 90% of all metals and mineral products consumed last year was recovered by open-pit mining. This has placed great pressure on this segment of the industry which has, consequently, resulted in some spectacular developments. With increasing size of projects, the need for increased sophistication of engineering, planning, management, and administration of modern mining installations has never become more apparent. The design of complete systems for the mine and plant that fit the mold of today&apos;s business and social environments is undergoing an evolutionary process. Traditional concepts in mine development and operations are being sidestepped in favor of new ideas and principles. As the overburden thickness increases, materials handling presents a major problem to mining companies, especially those concerned with the mass production of ore and waste from low-grade deposits. The profit margin here is likely to be significantly less as to take chances with capital investment. Constant efforts are needed to improve upon productivity if the ore is to be economically mined. The development of vast low-grade deposits and thick overburden deposits calls for better tools to handle the enormous amount of materials. A natural solution to this problem is the use of bucket wheel excavators (BWE), which employ a continuous cutting head to feed the materials handling system. High productivity, versatility, economy of operation, and adaptability to most types of haulage systems combine to make BWE&apos;s attractive for large earth-moving operations. "Operating costs are being pushed down by the impact of giant haulage units, by high-speed conveyors, and computerized railroads. Matching all these with the continuous output of BWEs, one can visualize increased production at much lower costs." Historical Background The wheel excavator, which was patented in Germany in 1913, made its first appearance in an open-pit lignite mine in 1920. From this early beginning, however, BWEs were slow coming into practice. Initial developments were dampened by many design problems. From 1936 onward, major developments in design improved the wheel&apos;s ability, capacity, and versatility. A literature survey shows that wheel excavators are being used in Australia, Zambia, South Africa, the Congo, India, Indonesia, Czechoslovakia, Russia, Great Britain, Guyana, Yugoslavia, Morocco, Germany, Canada, and the U.S. for mining and loading chalk, lignite, clay, sandstone, phosphate, broken ore of iron, coal, shale, loose and semi-loose rock overburden.&apos; A recent LMG* BWE at work in a German lignite mine weighs 6790 tons with an hourly capacity of 11,000 cu m. Although the BWE has wide applicability, its application to new mining areas poses a problem. Because of the large capital investment involved in BWE application and the narrow profit margins in mining low-grade ores or coal at depth, little margin of error can be tolerated in the selection, design, and operation of these machines. The questions that need to be answered prior to installation of a BWE for a mineable deposit are: 1.) What are the anticipated BWE performance characteristics? 2) Which method of BWE operation is most efficient? Attempts to answer these questions require a thorough knowledge of the mining system and the BWE operation. One approach is the building of a computer-ori-ented simulation model to determine how information and policy create the character of the BWE system under consideration. BWE Operation Modern BWEs generally excavate in blocks. Fig. la shows a BWE working in an established cut. The wheel is positioned to travel on the pit floor in line with the top edge of the old highwall. As it advances, a new highwall is exposed in the direction of excavation. Digging is done by rotating the wheel, swinging it from side to side in long parallel arcs, and "crowding" into the bank, by advancing the entire machine, or by the travel of the digging boom if an automatic crowd is available (Fig. lb). A second way by which the wheel can be advanced into the bank is by the falling cut method. A brief description of each of these methods follows. Cut with a Crowding Machine: At the end of every swing, the digging boom can be extended by the thickness of cut desired and the boom swung back in the reverse direction. Obviously, the thickness of bank excavated does not vary with the boom position; therefore, the slewing motion of the boom is fairly constant for uniform output. The thickness through which the digging boom can be advanced into the bank is theoretically calculated from the formula&apos;

Jan 1, 1971

By C. C. Templeton, J. C. Rodgers

A key step in feed water treatment for generating wet steam for thermal oil recovery is the removal of calcium and magnesiunt hardness by cation-exchange series softening. Knowing the solubility of any scale forming salts in brines at elevated temperatures is necessary for fixing the level to which the feed water must be softened. Such calcium sulfate solubility data, previously not available above 392F, were determined by the authors in a flow equilibrium apparatus mud will be reported elsewhere. These data were used to develop a method for predicting the solubility of anhydrite in hot water or steam droplets for saturated steam pressures as high as 2,000 psig (637F). (The calcium sulfate solubility product is represented by a combination of two factors, one reflecting the effects of ionic strength and the other accounting for the effects of complex ion formation in either calcium-magnesium-rich or sulfate-rich brines.) The method is applied to a calcium-magnesium-rich brine If moderately high salinity from a pilot hot-water flood, I nd to several sulfate-rich, low-salinity feed waters and l lowdown (cooled steam droplets) samples from steam s ak operations. The predicted calcium hardness levels corresponding to the calcium sulfate solubilities agreed reasonably well with the results of laboratory solubility determinations run on the field samples. Further testing of the method is needed for brines of other composition classes. Existing field cation exchange softeners in the cases tested are performing adequately since all the samples were found to be undersaturated with respect to calcium sulfate at their operating temperatures. Introduction Prevention of scaling caused by precipitation of calcium sulfate (anhydrite) is of considerable concern in connection with thermal recovery processes using wet steam or hot water. To avoid anhydrite precipitation in a heated system, an engineer must keep the product of the calcium and sulfate concentrations in the water or steam droplets below the value of the solubility product of anhydrite for the temperature and brine composition in question. Usually it is most practical to keep the concentration product lower than the solubility product by keeping calcium low in the presence of high sulfate, or by keeping sulfate low in the presence of high calcium. This can be done by a choice of combinations of natural waters and water treatment processes (such as series cation exchange softening to remove calcium). Until recently, few anhydrite solubility data, particularly for solutions containing other salts, were available for temperatures above 392F (211 psig steam); Marshall, Slusher and Jones&apos; studied the CaS0,-NaCI-H,O system up to 392F and surveyed the work of previous investigators. To model natural brines, one needs to study the solubility of anhydrite in aqueous solutions of sodium chloride, sodium sulfate, calcium chloride, magnesium chloride and their mixtures. Since steam pressures as high as 2,000 psig (637F) may be involved in thermal oil recovery projects, a solubility study was conducted between 482 and 617F.&apos; Discussed in this paper is the application of these data to the prediction of anhydrite precipitation in some practical steam soak and hot-water injection projects. Any simple method for predicting the solubility of an inorganic compound over a wide range of temperatures and solution compositions must be based on some assumptions, and therefore must yield approximate results. On the one hand, natural brines contain too many ionic species for all to be included in a simple scheme; on the other hand, there is no adequate theoretical basis for the exact prediction of solubility in even simple solutions of mixed electrolytes. However, it is possible at a given temperature to base a reasonable prediction scheme on two phenomena:&apos;-&apos; the increase in solubility with increasing total concentrations of all ions (as measured by the ionic strength; see the Appendix), and an increase due to formation of cornplexes between calcium ions and sulfate ions and between sulfate and magnesium ions. Stiff and Davis&apos; developed such a scheme for predicting the solubility of gypsum (CaSO, ¦ 2H,O) in brines at temperatures u~ to 212F. However, for the higher temperaturei of present interest, the stable solid phase is anhydrite (CaSO,). This study involves a two-part method for predicting anhydrite solubility products. First, one predicts a value K, for a given ionic strength I and a given temperature T corresponding to mo./msr, = 1 from data of the CaS0,-NaCI-H,O system. Second, one determines a group of factors F .= F(Ca) • F(Mg) • F(SO,), where the individual factors account for increases in the solubility product due to complex formation by high concentrations, respectively, of calcium, magnesium and sulfate. Combining the two parts, one obtains the solubility product in molalities as

Jan 1, 1969

By Thomas R. Smith

This paper covers oil shale resources in those countries that border the Pacific Rim. The major known resources around the Pacific Rim occur in the Western United States, Australia, the People&apos;s Republic of China, (PRC) and the Thailand/Burma region. The location of these deposits is shown in Figure 1. In 1965, the U.S. Geological Survey estimated world oil shale deposits of over 4 quadrillion tons having a potential oil yield of over 2 quadrillion barrels. If all this were extracted, it could meet the world&apos;s entire energy needs far into the future. However, the Survey also estimated the spent shale waste could cover all of the surface of the world to a depth of about 10 feet. Thus, for this and many other technical and economic reasons, it does not appear to be feasible to develop a large portion of the world&apos;s oil shale resources in this century; nor will shale in itself solve our energy problems. Nevertheless, shale oil and other &apos; synthetic fuels are expected to play an important role in new energy supplies in the longer term. WHAT IS OIL SHALE OR SHALE OIL? The term "oil shale" is sometimes a misnomer, in that the rock is often more of a limestone or siltstone than a shale. The common link between resources termed “oil shale" is that they all contain an insoluble substance cal led kerogen (which is from the Greek words for waxmaking). Kerogen is a form of organic carbon derived from a variety of plants ranging from algae to higher plants. When heated sufficiently, the kerogen generates hydrocarbons called shale oil, a form of synthetic crude oil that in most cases is lower in hydrogen content than conventional crude oil. The amount of oil in oil shale is relatively small --roughly 10 percent (by weight) in the richer shales. To upgrade this synthetic oil to usable products, additional processing is necessary. This brief sketch gives an idea of what this different, but significant, form of hydrocarbon is like. ENVIRONMENTS OF DEPOSITION Most oil shale deposits fall into three environments of sediment deposition: 1ake (called lacustrine), sea (marine) and river (fluvial-deltaic). In each case, the deposition of oil shales took place in quiet water environments where plant life, particularly algal plants, could flourish and, after dying, be deposited in unoxygenated water where the kerogen precursors would be safe from destruction by oxidation. The oil shales that were deposited in large lake basins (lacustrine) have attracted the most attention for development over the years. They often have multiple seams, deposited in a cyclic nature with extensive areal distribution and rapid vertical changes in kerogen content. Grades are moderate to high, ranging from 80 to 200 liters per tonne. Rundle in Australia and the Piceance Creek Basin in Colorado are examples of this type. Both deposits represent large volumes of oil shale in small areas which could provide the large volume of feedstock needed for future commercial operations. The stratigraphic sections of these two deposits feature thick oil shale seams with average grades of 80 - 125 liters/tonne conducive to both open pit, and underground operations. However, the rock strength of the Rundle shale is not sufficient to - support underground mining. On the other hand, the Colorado deposits, being more carbonate in nature, are sufficiently strong to support either type of mining depending on the overburden to ore ratio. These latter types of deposits will likely provide the first target for development of a commercial industry. The marine type is characterized by extensive areal distribution with relatively thin seams. The grades are generally low to moderate, ranging from 50 to 120 liters per tonne. The marine oil shales are common worldwide, and their attractiveness for mining is dependent on the overburden to ore ratio. Because of their widespread areal distribution, their in situ resources can be quite large. The Toolebuc Formation in Central , Queensland, Australia is a good example of this type of deposit being 7-10 meters thick over an extensive area. The Julia Creek deposit with its favorable overburden-to-ore ratio is being studied for possible development. In a fluvial-deltaic environment, there are many small lakes or bogs associated with rivers in which a very pure type of oil shale called torbanite could form. Torbanites are very high grade containing up to 75 percent hydrocarbons. The known occurrences are generally small lenticular deposits associated with coal seams. Even with the high grades, it is not likely that any of the known deposits would warrant commercial development because of their small size. The torbanite deposits in New South Wales, Australia were processed prior to World War I1 near the town of Glen Davis. However, today&apos;s known resources of this type are not large enough to warrant a commercial plant.

Jan 1, 1982

By E. W. Felegy

THE need for improved mine communication to increase efficiency and to insure greater safety has long been recognized. General and unrestricted communication between all points underground, and between the surface and all points underground, is probably the least advanced phase of the mining industry. An ideal system of mine communication must require no fixed wire installations. The equipment must be small, lightweight, and readily portable, and the power requirements low. A system that can be used not only under normal circumstances but also in an emergency, when the continuity of wires, tracks, and pipelines may be disrupted, must function independently of any aid furnished by standard installations. Radio communication offers possibilities of meeting all the requirements necessary for an ideal communication system in underground mines. Transmission of signals must be achieved through one or both of two mediums, through the air in mine openings or through the strata. The results or lack of results obtained by early investigators showed conclusively that radio communication by space transmission cannot be accomplished effectively beyond line-of-sight distances in underground passageways. A radio system underground therefore must depend solely upon transmission through soil and strata. The application of radio to underground mine communication was investigated by many individuals and agencies at different times in the last several decades, but little success was achieved before World war 11.2-0, The results of experiments during the war, and further knowledge gained in experiments with vastly improved communication methods and equipment after the war provided the background for additional research in radio communication in underground mines. During 1950 to 1.952 the University of Minnesota sponsored an investigation to determine the possibility of developing: a system of radio communication universally applicable in underground metal mines in the Lake Superior district. The possibility of using radio equipment to determine the imminence of rock bursts in deep copper mines in that district also was investigated. The investigation supplemented previous and concurrent emergency mine communication studies of the U. S. Bureau of Mines. Testing equipment and laboratory facilities maintained by the Bureau of Mines at Duluth, Minnesota, were used in the research program, which was conducted as a mining engineering graduate research problem by the present writer under the direction of T. L. Joseph and E. P. Pfleider. The radio units used in the research program were designed and built to specification solely to conduct tests of radio communication in mines. Two identical units were used in all tests. Each unit contained a transmitter section, a receiver section, and a power-supply section, mounted on a single chassis. The entire unit was enclosed in a single 10x12x18-in. metal case provided with a leather-strap handle for carrying purposes. The front of the case was hinged to open upward and provide easy access to the single control panel on which all controls were mounted. Storage batteries supplied the operating power for all tests. Standard 6-v automobile batteries were utilized to provide adequate capacity to conduct tests for a full day without exhausting the battery. A frequency range from 30 to 200 kc was covered in eight pre-fixed steps on each unit. The carrier frequencies were crystal-controlled and amplitude-modulated. The receiver employed an essentially standard superheterodyne circuit and was sufficiently sensitive to detect signal strengths of 5 micro v. A heterodyne circuit was employed in the transmitter to obtain the low-carrier frequencies used in the units. Power output of the transmitter, usually less than 2 w, rarely exceeded 3 w in any test. Tests were conducted in mines on the Vermillion iron range in Minnesota, the Gogebic iron range in Wisconsin, the Menominee and Marquette iron ranges in Michigan, and a copper mine in the upper Michigan peninsula. All tests were conducted when the mines were operating normally, and usual mining, maintenance, and transportation activities were in progress, so that any interference caused by normal production activities could be evaluated during the tests. Tests were made between different points underground in each mine, and between underground and surface points at some mines. Test readings obtained at any one mine were calibrated in the laboratory before another series of tests were begun at the next mine. The transmitter and receiver were separated by one or more levels in each test, and generally there was no other means of communication between test points. Two 100-ft lengths of rubber-covered wire were used for antenna wires on each unit in both transmission and reception. The ends of the wires were connected to ground points in one of several methods, depending upon physical conditions at each test site. The wires were clipped to metal rods about 200 ft apart in the back, side, or bottom of the mine opening where the character of the rock permitted driving rods. Both wires were clipped to points about

Jan 1, 1954

By L. C. Brown, S. K. Behera

The diffusion rate in Ag-Sb couples is sensitive to con~pressive load with the width of Ag3Sb, the only phase present in the diffusion zone, increasing with stress up to 800 psi and remaining constant above this. Kirkendall marker experiments show silver to diffuse much faster than antimony in Ag3Sb and incipient porosity may therefore develop at the Ag/Ag3Sb interfnce restricting the transfer of atoms from the silver into the diflusion zone. Application of compressive stress reduces the tendency for porosity to develop and so increases the growth rate. In a recent paper Brown et al.1 observed a significant increase in the thickness of Cu2Te in Cu-Te diffusion couples on application of a compressive stress as low as 20 psi. Similar stress effects have also been observed in the Fe-A1,2 Al-u,3 arid cu-sb4,5 systems. It has been suggested that the increase in growth rates of intermetallic phases in these systems is due to a decrease in the amount of Kirkendall porosity with applied stress. In the present paper, results are presented of the effect of compressive stress on diffusion in Ag-Sb, together with a detailed examination of the Kirkendall effect. The Ag-Sb phase diagram6 shows that antimony has a moderate degree of solid solubility in silver, 5.7 at. pct at 350°C, but that there is essentially no solubility of silver in antimony. There are two intermediate phases— (hcp7) from 8.8 to 15.7 at. pct Sb and Ag3Sb (orthorhombic8) from 21.8 to 25.9 at. pct Sb. EXPERIMENTAL Diffusion couples were prepared from fine silver of 99.95 pct purity and from antimony of 99.7 pct purity. Both the silver and antimony were produced in the form of discs 1/2 in. in diam by approximately $ in. thick, with surfaces ground flat to 3/0 emery paper. Diffusion anneals were carried out in the apparatus previously described.1 A compressive load was applied to the diffusion couple through a lever arm system, with a reproducibility estimated to be ±10 psi. All runs were carried out in a protective hydrogen atmosphere. Following the diffusion anneal specimens were sectioned and polished and the width of the diffusion zone was measured metallographically. Composition profiles were measured using an electrostatically focused electron probe with a spot size of 10 , counting on Sb L radiation. Corrections for matrix absorptiori and fluorescent enhancement9 were not required. S. K. BEHERA, formerly Graducate Student, Department of Metallurgy, University of British Columbia, is now Postdoctoral Fellow, Whiteshell Nuclear Laboratories, Atomic Energy of Canada Ltd., Pinawa, Manitoba. L. C. BROWN, Junior Member AIME, is Associate Professor, Department of Metallurgy, University of British Columbia, Vancouver, B.C., Canada. Manuscript submitted June 14, 1968. IMD RESULTS Fig. 1 shows an electron probe traverse of a typical diffusion zone. In all couples examined only one intermediate phase was observed and the composition of this phase, 23 wt pct Sb, was in good agreement with the composition of Ag3Sb, 23 to 28 wt pct Sb. The presence of this phase was confirmed by X-ray diffraction of filings taken from the diffusion zone. The probe traverses showed no detectable solid solubility in either the silver or the antimony although the phase diagram indicates that some antimony, up to 6.5 wt pct pct Sb, should be in solid solution in the silver. However the width of this portion of the diffusion zone would be expected to be very small in view of the low diffusion coefficient in the silver, 4 x 10-l6 sq cm per sec at 350°C, 10 compared with that in the Ag,Sb, estimated as 3 x 10-8 sq cm per sec in the present work, and this region would therefore not be expected to be seen in the probe traverse. Application of stress resulted in a significant increase in the width of the diffusion zone, Fig. 2. At 350°C, the thickness of Ag3Sb increased from 250 at 0 psi to 400 p at the limiting stress of 800 psi, indicating an apparent 150 pct increase in the diffusion coefficient. Similar behavior was also observed at 400°C, indicating that the stress effect is not characteristic of just one temperature. The growth of Ag3Sb at 350°C and at various stresses is shown in Fig. 3. In every case the growth rate was parabolic indicating diffusion control. The kinetic curves all passed through the origin showing that delayed nucleation of Ag3Sb was not responsible for the stress effect and that it was a real growth effect. A series of tests were carried out in which diffusion was allowed to take place at a lower stress following an initial high stress diffusion anneal. Speci-

Jan 1, 1969

By A. F. Henderson, C. F. Cornell, A. F. Dunyon, D. A. Dahlstrom

Ossi E. Palasvirta (Development Engineer, Oliver Iron Mining Diu., U. S. Steel Gorp.)—The authors are to be congratulated for their interesting article, which thoroughly illustrates the variables inherent in filtration of taconite concentrate. The work and the conclusions based thereon largely parallel the test work done by the writer at the Pilotac plant" and the experience gained with a commercial size agitating disk filter in the same plant. At Pilotac, however, a thorough study was also made of the effect of depolarizing (demagnetizing) the filter feed, and it is the purpose of this discussion to comment on the merits of depolarization of the magnetite concentrate prior to filtering. The work at Pilotac was done in three phases: 1) preliminary laboratory testing with a circular filter leaf of 0.047 sq ft, followed by 2) plant testing using a 4-ft diam, single-disk agitating filter that was purchased on the basis of the pilot tests on the 4-ft model. In the laboratory tests depolarization was achieved by slowly withdrawing&apos; batches of thickened concentrate from a coil producing an alternating field of about 300 oersteds. In plant tests the standard Pilotac procedure&apos; was employed, wherein the pulp falls freely through the depolarizing coil. The preliminary tests in the laboratory at first seemed to indicate that although depolarization of the filter feed decreases the cake moisture, it also tends to decrease the thickness of the cake, thus decreasing filtering rate. The tests with the 4-ft disk filter soon showed, however, that the compactness of the cake, attained during the form period because of depolarization, permitted a considerable decrease in drying time without any sacrifice in final moisture content. Thus, the filter could be operated at a much higher speed, and the overall capacity was higher than with magnetized feed. Because of the great compactness of the cake there was little shrinkage during the drying period, which prevented cracking and subsequent loss in vacuum. This in turn permitted operation with as thick a feed pulp as the diaphragm pumps could handle, eliminating the necessity of pulp density control. On the basis of these findings, the 6-ft agitating disk filter has been operated at 2 rpm, using feed pulps varying from 65 to 73 pct solids. Initially Saran 601 was used as medium, but it was later replaced with a relatively open, tight-twist nylon cloth. Filtering rates up to 750 lb per ft- er hr can be attained with feeds averaging about 70 pct- 270 mesh, and there is no trouble because of cracking. The cake moistures vary between 8.5 and 9.5 pct. To recapitulate, the merits of depolarizing the filter feed may be summed up as follows: 1) The well dispersed pulp shows less tendency to settle in the filter tank. 2) The homogeneous filter pool results in more even cake formation. 3) Because of absence of flocs, great compactness of cake is attained during the form period. 4) The cake does not tend to crack during the drying period. 5) A drier cake is produced. 6) A shorter drying period is necessary, permitting higher operating speed, which in turn results in increased capacity. 7) Density of the feed pulp can be kept as high as the equipment can handle. This increases capacity, since it is directly proportional to the percentage of solids in the pool. A few tests were also made to study the effect of chemical flocculants on filtration efficiency. Results showed that the effects of chemical and magnetic floc-culation were quite similar. Thus the use of a floccu-lant would impair rather than improve the filtering of magnetite concentrate. A. F. Henderson, C. F. Cornell, A. F. Dunyon and D. A. Dahlstrom (authors&apos; reply)—We want to thank O. E. Palasvirta for his comments, particularly in view of the encouraging results obtained with demagnetized taconite concentrate. In our studies an attempt was made to evaluate the effects of depolarizing the feed to the plant filters by passing the slurry through a coil, similar to the method described by Palasvirta. Unfortunately, in our experiments there were no startling improvements in performance level, neither cake rate increase nor cake moisture reduction. However, when slow filter cycle speeds were employed, the filter cake tended to crack and the vacuum level dropped, resulting in an increase in cake moisture content. When demagnetized feed was used during slow speeds, no cake cracking was evidenced and the vacuum level remained constant. Thus the depolarizing coil was found necessary only in cases of cracking. It should be noted that most of our test work concerned a feed of 85 to 90 pct —335 mesh and about 60 pct by weight solids concentration. This contrasts with 70 pct —270 mesh and 65 to 73 pct by weight solids as noted by Palasvirta. Reviewing both sets of results, it might be concluded that depolarizing may be successfully employed to alleviate cake cracking tendencies and may markedly improve cake rates and moistures on the coarser taconite concentrates. Further investigations may disclose the exact relationship of grind and pulp density to the depolarizing action.

Jan 1, 1959

By T. Y. Yan

SUMMARY Laboratory high pressure column tests have shown that the presence of 1-20 ppm of aluminum ion effectively prevents permeability loss during uranium leaching with leachates containing sodium carbonate. If added after permeability loss has occurred, aluminum ion can restore the permeability to nearly its original value. No deleterious effect was observed on uranium leaching performance and the technique should be quite compatible with all field operations. INTRODUCTION The recovery of uranium values from underground deposits by in situ leaching or solution mining has become economically viable and competitive with conventional open pit or underground mining/milling systems (Merrit, 1971). In situ leaching processes are particularly suitable for small, low-grade deposits located in deep formations and dispersed in many thin layers. Many such ore bodies occur along a broad band of the Gulf Coastal Plain (Eargle et. al., 1971). The advantages of the in situ leaching processes have been reviewed (Anderson and Ritchi, 1968). In the in situ leaching process, a lixiviant containing the leaching chemicals is injected into the subterranean deposit and solubilizes uranium as it traverses the ore body. The pregnant lixiviant or leachate is produced from the production well and is then treated to recover the uranium. The resulting barren solution is made up with the leaching chemical to form lixiviant for re-injection. Upon completion of the leaching operation, the formation is contaminated with leaching chemicals and other species made soluble in the leaching operation and has to be treated to reduce the concentration of these contaminants in the ground water to levels acceptable to the regulatory agencies (Witlington and Taylor, 1978). Restoration is accomplished by injecting a restoration fluid, which could be the fresh water or water containing chemicals, into the formation. As it traverses the leached formation, the restoration fluid picks up the contaminants and is then produced at the production well. This produced water is either disposed or purified for recycle. In both phases of operation, formation permeability or well injectivity is one of the most important parameters which determines the viability of the in situ leaching process. Low formation permeability limits production rates, leading to uneconomical operations. The formation is said to be sensitive if there is a sharp loss of permeability on contact with water and other fluids. Many uranium bearing formations, for example, the Catahoula formation of the Texas Coastal Plain, contain significant amounts of clay minerals which are water sensitive. Serious permeability losses can occur when the pH and chemical composition of the lixiviant is significantly different from that of the formation water. Jones has investigated the influence of chemical composition of water on clay blocking of permeability (Jones, 1964) and Mungan studied permeability reduction through changes in pH and salinity of the water (Mungan, 1965). Various mechanisms of permeability damage have been proposed and reviewed (Jones, 1964; Mungan, 1965; Gray and Rex, 1966; and Veley, 1969). When large amounts of swelling clays are present, a significant fraction of the flow channels in the formation can be reduced due to swelling. However, in most cases, swelling need not be the main cause of permeability losses. Particle dispersion and migration or clay sliming can be more important causes for formation damage. Clay particles entrained in the moving fluids are carried downstream until they lodge in pore constrictions. As a result, microscopic filter cakes are formed by these obstructions, plugging the pores, effectively restricting fluid flow and reducing the formation permeability. Moore found that as little as 1-4 percent clays present in a fine grained sandstone could completely plug the formation if they are contacted by incompatible injected fluids (Moore, 1960). It has been found that injection of NaHC03/Na2CO3 lixiviant into formations with significant clay content often leads to loss of formation permeability and well injectivity. To alleviate this problem a change of the lixiviant composition to KHC03/K2CO3 has been proposed. At present, however, many in situ leaching operations employ NH4HC03/(NH4)2C03 mixtures as a source of carbonates. This approach has been successfully used in South Texas by Mobil, Intercontinental Energy, Wyoming Minerals and U.S. Steel, etc. The use of ammonium carbonates solutions, however, contaminates the formation and requires a time-consuming restoration operation. The other approach to reduce the permeability loss is to pretreat the sensitive formation with chemicals which prevent clay dispersion and migration. Such chemicals include hydroxy-aluminum (Reed, 1972 and Coppel et. al., 1973), hydrolyzable zirconium salts (Peters and Stout, 1977), hydrolyzable metal ions in general (Veley, 1969) and polyelectrolyte polymers (Anonymous). Still another approach, is to minimize the "shock" caused by sudden injection by gradually changing the chemical composition of the injected fluids from that of the formation water. THE APPROACH Since permeability loss can be an important factor limiting the efficiency and economic viability of the in situ leaching process, a study was initiated on

Jan 1, 1982

By D. Turnbull, J. C. Fisher

ACCORDING to the "reaction-path" modell,2 of martensite nucleation, the shear angle of the embryonic martensite plate must be treated as a variable, and included in any calculation of nucleus critical size. Also, as can be deduced from this model, the interfacial free energy between austenite and martensite does not reach its final value until the shear is completed. It is zero for zero shear angle. However, in order to account for the kinetics of the martensite transformation, some sort of interfacial energy barrier appears to be necessary even with the reaction-path model, for otherwise the volume and the energy of formation of the critical size nucleus both collapse to zero.3 Cohen independently suggested that surface energy could be incorporated into the reaction-path model, with the overall free energy of a martensite embryo being a function of its volume and shear angle.&apos; It is possible to estimate the energy associated with the formation of a critical-size martensite nucleus starting with the reaction-path model and including a surface free-energy barrier. As the dependence of interfacial free energy upon shear angle is unknown, a simple type of dependence will be assumed, with the belief that the true dependence would not lead to appreciably different results. Consider the work required to form a lenticular martensite plate with radius r, thickness t, and shear angle 8. There are three contributions; one being the interfacial free energy, one being the free energy change in the martensite plate, and one being the free energy increase in the surrounding austenite. The interfacial free energy u is assumed to depend upon the shear angle 0 according to the relationship s=s0(?/?0)n [1] where 8, is the equilibrium shear angle and n is an exponent that may lie in the range 0 n 2. The work required to form the interfaces of a martensite plate then is W. = 2pr² s0(?/?0)n [2] The free energy change per unit volume of martensite is composed of two parts, one the ordinary volume free energy ?f1. which is negative, and the other the elastic strain energy G?m²/2, where G is the shear modulus and 7, the shear strain relative to the martensite structure. This expression for the strain energy is valid only when the shear strain ym, is sufficiently small that the martensite is within its linear elastic range. There is no doubt that ym, lies beyond the linear elastic range for embryos that are considerably subcritical. However, for critical nuclei it will be shown that ym, is 1.5 pct or less, within the linear elastic range of martensite. For embryos of nearly critical size, then, the strain energy of the martensite is correctly given by G?m²/2. The shear strain in the martensite is ym, = 8, — 8, and the work required to form the strained martensite is Wm --= (pr²t/2) [?fv + G(?O - ?)²/2] [3] The free energy change in the austenite is entirely that due to elastic distortion. The elastic strain is not uniformly distributed in the austenite, being large near the martensite plate and small elsewhere. Approximately, however, the energy corresponds to a uniform shear strain ya= (?t/2)/r [4] throughout the volume 4pr³/3 surrounding the plate. The work required to strain the surrounding austenite then is Wa = (4pr³/3) (G?a²/2) = (G?²/6) prt² [51 For simplicity, the same shear modulus G is assumed for each structure. The total free energy for forming a plate then is W = W3 + Wm + Wa. = 2pr² s0 (?/p?0)n + (pr²t/2) [?fr+G(?0-?)²/2] + (G?²6) prt2 [6] This expression is correct for nuclei and for embryos of nearly critical size, where, as will be shown, the strain energy in the martensite is correctly given by the expression G (? — ?)². Having W as a function of r, t, and 8, as in Eq. 6, there is a saddle-point where W has a stationary value, W subsequently decreasing indefinitely as the nucleus volume increases along the reaction path. The stationary value of W is the energy of the critical nucleus. The critical nucleus has radius, thickness, and shear angle such that ?W/?r - awlat: = ?W/?p? = 0. Performing these differentiations and calculating the critical nucleus energy, W* = [8192p(G?/6)²;s/27 ?fv4] [7] where a= (?/?0)3n+1[l +G(8"-8)&apos;/2af.]&apos; [7a] and where 8 is to be determined from the equation (1 + 3n/4) + G8(6O - (9)/[Af. +G(6>o-6>)72] = 0 [8] For ?f, near —200 cal per mol or —10" ergs per cc, and 8, near 1/6, as for iron-base alloys, Eq. 8 gives ?0 - ? ~ - (4 + 3n) ?f1./4G0O [9] as the difference between the equilibrium shear angle and the actual shear angle for a critical nu-

Jan 1, 1954