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By Thomas E. Garnar

Zirconium and hafnium are curious elements because they are almost always found together in nature. Zirconium was discovered by Klaproth in 1789 and isolated 35 years later by Berzelius. Because hafnium's chemical properties are so close to those of zirconium, it was not discovered until 1923 when Coster and Von-Heresey detected it using x-ray spectrographic analysis. These elements occur most commonly in nature as the mineral zircon (ZrSiO4) and less commonly as the oxide baddeleyite (ZrO2). They also are found as a variety of other silicates. Zircon was identified as a component in alluvial and beach sands in 1895, but it was not produced in any quantity until 20 years later. Zircon is always a coproduct from TiO2 mining and processing. During World War I it was produced as a coproduct of beach sand mining for titanium minerals just south of Jacksonville Beach, FL, and was patented as a refractory. It was not until the 1930s when Zircon Rutile, Ltd. began mining at Byron Bay on the east coast of Australia that zircon was first used as a foundry sand. Later in the 1940s, NL Industries, Humphreys Gold Corp., and E. I. du Pont de Nemours & Co., Inc. began production of zircon sands from fossil beaches in northeast and northcentral Florida. Baddeleyite first became available as a commercial product in 1916, but never in the quantity of zircon. Zircon holds a unique position as an industrial mineral because it is used for both its physical and chemical properties as well as an ore of zirconium and hafnium metals. Australia is the major zircon producer followed by South Africa and the US. Zircon is also produced in India, Sierra Leone, Sri Lanka, Malaysia, China, Thailand, and Brazil. Undeveloped heavy mineral beach sand reserves containing zircon are known to occur in Egypt, Malawi, Senegal, and Tanzania. Locations are shown in Fig. 1. Mineralogy Zirconium and hafnium are always present together in naturally occurring compounds. Most commonly they form as the silicate sometimes containing iron, calcium, sodium, manganese, and other elements. Less commonly they are found as oxides in combination with titanium, thorium, calcium, and iron. Zircon is the most common form. It is extremely resistant to weathering, therefore, often it is present in ancient beach sands and placer deposits. Although resistant to alteration from external sources, it is vulnerable to internal alteration as the result of thorium and uranium substituting for zirconium either in the zircon lattice or in solid solution. Alteration to the metamict state takes place as radioactive emanations from these elements disorder the crystal lattice, accompanied by hydration, reduction in specific gravity, and changes in color. The mineralogy of zircon and baddeleyite and variation of physical and chemical properties are shown in Table 1. The effects of zircon's internal alteration and darkened color can be corrected by heating to 1000°C for 30 min or so. A certain time-temperature relationship makes it possible for decolorization and reordering of the crystal lattice to take place when heating at higher temperatures for shorter periods or at lower temperatures for longer periods. After heating, x-ray diffraction patterns are sharper, the grains may be harder, and except for particles of malacon, the grains will be white or colorless in the absence of grain surface coatings. The color change is only temporary and the particles slowly darken with time. Zircon fluoresces light yellow in shortwave ultraviolet light. If exposed to ultraviolet light for extended periods of time, white (calcined) zircon turns purple. With time the induced color begins to fade and eventually disappears (e.g., calcined Florida zircon exposed to ultraviolet light for 24 hr still retains faint, but discernible, purple color after six months).

Jan 1, 1983

By Oliver Bowles

Dimension stone is a term applied to stone sold in blocks or slabs of specified shapes and usually of specified sizes, contrasted with crushed, broken and pulverized stone covered in another chapter. Dimension stone includes cut stone, rough building stone, ashlar,* rubble, monumental stone, paving blocks, curbing, flagging, and many types of ornaments and novelties carved from stone. Riprap-large, irregular blocks used for shore protection-is classed with crushed and broken stone. Composition, Varieties, and Properties Dimension stones are of many kinds. The principal varieties are granites, trap rock (diabase, basalt, and gabbro), sandstone, limestone, and marble. Slate is covered in a separate chapter. Granite is a visibly granular crystalline rock consisting essentially of feldspar, quartz, and mica or hornblende. The basaltic rocks are darker in color than the granites. They contain little or no quartz and consist largely of plagioclase feldspar, augite, pyroxene, and hornblende. They are classed commercially as black granites. Limestone consists essentially of calcium carbonate. Dolomites and magnesian limestones used as dimension stone are classed with the high-calcium limestones. Marble is a crystalline form of limestone, but in the trade, any carbonate rock which will take a polish is called a marble. Many limestones which are fossiliferous but which will take a polish are sold as a decorative stone for lobbies of hotels and office buildings. Sandstone consists essentially of silica in the form of sand grains cemented into a coherent mass. Although rock occurrences are numerous and widespread, the exacting requirements of use condemn all but a small fraction of them for commercial use as dimension stone. No deposit that has closely spaced joints or planes of weakness can be used because sound blocks of moderate to large size are demanded. Uniform texture and grain size, constant and attractive colors or color pattern, and freedom from impurities that may cause stains or deterioration usually are demanded. Hardness is a variable property. Granites and diabases are as hard as or harder than steel, while limestones and marbles may be scratched with a knife. The hardness of sandstone depends upon the degree of cohesion of the grains. Workability depends to a considerable extent on hardness, but the degree of hardness has little influence on use except where stones are subjected to abrasion as on steps or floors. "Texture" as applied to stone relates to the arrangement, uniformity, and size of the constituent grains. Stones are of many colors and thus can satisfy a variety of tastes. For monumental stone, a marked contrast between polished and tooled surfaces is preferred in order that inscriptions may be read easily. Strength requirements usually may be disregarded because any sound structural stone suitable in other respects is almost invariably many times as strong as would be required for any ordinary use. The pressure on the base course of the Washington Monument, Washington, D. C., is less than 700 psi, and highgrade granites, limestones, sandstones, and marbles will sustain a crushing load of 10,000 to 25,000 psi. A structure made of stone with a crushing strength of 15,000 psi would have to be nearly 21h miles high before crushing of the lower courses would occur. However, stone disintegrates more readily under severe

Jan 1, 1960

By O. R. Wagner, R. O. Leach, H. W. Wood, C. F. Harpke

PAN AMERICAN PETROLEUM CORP.TULSA, OKLA. CASPER, WYO A field test has been made in which additional oil recovery was obtained from a previously-waterflooded "oil-wet" sandstone reservoir. This recovery improvement was accomplished by adjusting the reservoir wettability through chemical treatment of the flood water. The test was made in the Muddy sand of the West Harrisburg Unit, Neb. The chemical used, sodium hydroxide, was injected as a slug of dilute caustic solution through a water-injection well. The natural wettability of the reservoir and the chemical requirements for reversing wettability were determined in the laboratory from contact-angle studies using field water and oil samples. Laboratory flood tests with a synthetic system had shown that reversing the wettability of an oil-wet consolidated core would lead to improved oil recovery. The field performance indicates that the mechanism by which increased oil retovery is obtained in the field is the same as that observed in the lahoratory. Laboratory studies indicate that higher ultimate recoveries and decreascd water-injection requirements result when the adjusting agent is added early in the life of the flood. However, a previously waterflooded area was intentiorzally chosen for the field test so that unambiguous conclusions could be made about the effects of chemical injection on wettability and the extent of oil-recovery improvernent afforded by wettability reversal. Forces existing at the fluid-solid and fluid-fluid interfaces in a porous medium have an important effect on oil recovery during a water flood. Modifying these interfacial forces in the reservoir to improve oil recovery has been the object of much research. Several papers' ' have discussed the use of surfactants to lower the water-oil interfacial tension. This paper describes work concerned with improving oil recovery by modifying the forces at the fluid-solid interfaces— that is, by changing the preferential wettability. An earlier paper: presented evidence to show that some reservoir systems could be changed from preferentially oil-wet to preferentially water-wet by the action of simple chemicals added to the water to increase waterflood oil recovery. The process was attractive for further study because it used only inexpensive chemicals and because it called for a gross "wettability reversal" rather than for a precise adjustment. The present paper is an extension of the earlier work. Laboratory flow tests were made using treated water and oil in a consolidated core to determine the amount of additional oil recovery and the producing performance which might be expected from reversing the wettability of an oil-wet reservoir during a flood. A contact-anglc study using water and oil from the Muddy "J" sand of the Harrisburg field, Banner County, Neb., indicated the reservoir to be preferentially oil-wet and susceptible to wettability reversal through chemical injection. Based on these studies, a field trial of wettability-reversal water flooding was initiated. in the Harrisburg field. The primary purpose of the trial was to determine if wettability-reversal flooding would improve oil recovery in an actual field situation. The field trial was also an important test of the laboratory tecnique used to determine the effect on oil recovery of certain wettability manipulation, as well as a test of the contract-angle method of determining reservoir wetra-bility. The paper is presented in two parts. The first part covers the laboratory experiments leading up to the field trial, and the second part covers the field trial. PART I—LABORATORY STUDY The laboratory experiments consisted of displacement tests using an idealized fluid system and of a contact-angle study with crude and water from the Muddy "J" sand of the West Harrisburg Unit, Banner County, Neb. The displacement tests were designed to determine the effects of a particular wettability manipulation, oil-wet to water-wet, on oil displacement in a water flood. The contact-angle measurements were made to determine the natural wettability of the reservoir and to determine if beneficial wetting changes could be brought about by a chemical addition to the flood water. PROCEDURE DISPLACEMENT TESTS The displacement tests were perfornled in a consolidated sandstone core using a refined oil and water. The wetting properties of this system could

By D. D. Pollock

Many constitution diagrams do not indicate the limits oJ solid solubility of the silver-rich solid solutions below 200°C. Thermoelectric measurements were employed to determine this limit in the nieighborhood of room temperature. The appearance of a second phase causes a discontinuity to occur in the tkevtrroelectric power as a function of cornposition at constant temperature and pressure. This discontinuity was employed to determine the limits of the silver-rich terzinal solid solutions of the Ag-A l, Ag-As, Ag- Bi, Ag--Ge, Ag-In, Ag-Pb, Ag-Sb, and Ag-Sn systenls at 30°C. CONSIDERABLE work has been done on the constitution of binary alloys of silver. The available data have been compiled by Hansen1 and Elliott.2 However, many of the binary diagrams do not show the limits of solid solubility of the silver-rich solutions below about 200° C. This work was undertaken in an attempt to extend these limits to the neighborhood of room temperature . PREPARATION OF ALLOYS All of the alloys were made with silver containing less than 0.014 pct (by weight) of impurities. The materials were weighed out into 225-g heats and melted in a high-frequency induction furnace. The indium, tin, and antimony alloys were melted in A1203 crucibles, under a boric anhydride cover, and were poured into split graphite finger molds. The aluminum, germanium, arsenic, lead, and bismuth alloys were melted in machined graphite crucibles; they were also covered with boric anhydride and poured into split graphite finger molds. The $-in.-diam ingots were heated to 750°C and were forged and hot-rolled down to 0.1 by 0.1 in. The wires were pickled in a 25 pct HNO3-75 pct H2O solution to remove any oxygen-rich surfaces. The wires were then annealed at 550°C for 2 hr in a dissociated ammonia atmosphere. They were then furnace-cooled for 20 hr to room temperature in this atmosphere. The wires were cold-drawn to 0.0808 in. diam. The finished wires were again annealed at 550°C in the same manner as in the first anneal. Thermoelectric Power. The thermoelectric power of a single specimen of each alloy was determined against pure silver which contained a maximum impurity content of 0.014 pct by weight. The wire specimens were straightened and then cleaned with ethyl alcohol. They were then reannealed in the same way as the finished wires to assure that any residual stress would be at a minimum level. Previous work has shown that the presence of small amounts of stress has the effect of decreasing the thermoelectric power. The alloy specimen was soldered to the pure silver wire to form the measuring junction. A standard set of copper leads was then soldered to the reference junctions of the thermocouple. These junctions were maintained in separate dewar flasks which contained finely shaved melting ice during the test. The thermal electromotive forces of the thermocouples were measured at four temperatures between 15° and 45°C. A known source of electromotive force was balanced against the output of the thermocouple until a null balance was reached. The data were then expressed in terms of the thermoelectric power at 30°C. The results were then converted to absolute thermoelectric power, s303.3 These data have an average error of less than ±0.2 pct. RESULTS AND DISCUSSION All of the experimental data are given in Table 11. Since the electromotive forces of the binary alloys of silver were determined against the pure silver from which they were made, the resultant thermoelectric powers are only a function of the intentionally added binary elements at the constant test temperatures. This provides a direct measure of the effects of the alloying elements. The absolute thermoelectric power of an alloy of silver is given4 by:

Jan 1, 1968

By W. O. Philbrook

An engineering analysis indicates that the coke rate in present blast-furnace practice is set not by chemical or thermal needs but to give adequate charge permeability for economical driving rates. An equation showing interrelations among pressure drop, gas flow, and charge characteristics has been derived. Flooding conditions and the location of the fusion zone are discussed. Maximum ore size is probably limited by chemical re-ducibility rather than by heat transfer. THE intention of this paper is to show that the ].imitations on the production rate and coke requirement of the iron blast furnace are not primarily chemical or thermal in nature but are related to characteristics of the burden and operation that govern gas flow, heat transfer, and stock movement. A semiquantitative analysis will be developed in terms of standard engineering principles to give a useful picture of the relative importance of physical and mechanical factors in contrast with the chemical features of the process that are more commonly emphasized. Most of the details of calculation have been omitted in the interest of brevity and to avoid submerging the rnain points in a sea of arithmetic. Numerical values have been arrived at by objective methods from reported operating data or by reasonable estimates of material properties where exact data are lacking and then tested to see how well they fit practice, rather than by working backward to find what assumptions are needed to give the desired answers. The analysis is oversimplified in many ways because exact engineering relations have not yet been studied for bed distributions as complex as are known to exist in the blast-furnace stock column. One objective of this paper is to show that the blast furnace, in spite of its complexity, can be at- tacked by engineering methods in the hope that this viewpoint will stimulate the kind of research needed for a more exact treatment. The basic ideas and many of the conclusions presented are qualitatively well known. A careful literature survey to credit the source of all observations not original to the author would indeed be voluminous, and such has not been attempted. T. L. Joseph's Howe Memorial Lecture' gives an excellent background of what is known about the internal workings of a blast furnace. Other important reference works or sources of specific information will be noted. It is hoped that the present paper will contribute something new, in method of attack and interpretation, that will aid in a clearer understanding of how to operate the blast furnace to best advantage. Factors Limiting Production and Coke Rates The rate of combustion of coke in a blast furnace, as in any fuel bed, is exactly proportional to the rate at which air is supplied. It is axiomatic, then, that the production rate of a furnace is limited by the rate at which it will take wind, i.e., burn coke, and the amount of coke that must be burned at the tuyeres to make a ton of iron of suitable composition. These two possible limiting factors will be considered briefly in the order mentioned. One common restriction on wind rate is flue-dust production. Since the volume of top gas is nearly proportional to the blast volume (by a factor of about 1.35 on a dry basis), an increased wind rate causes a correspondingly increased linear velocity of top gas in the throat of the furnace. The higher

Jan 1, 1955

By George Simkovich

It was hypothesized that solid-state point defects should alter the flotation properties of solids. Tests conducted on pure AgCl and AgCl doped with CdC12 show that atomic point defects exhibit an important role in the floatability of AgC1. Tests conducted on PbS doped with Ag2s or Bi2S3, also show that the defect structures resulting from these dope additions, i.e., a combination of electronic and atomic point defects, contribute significantly to the flotation of PbS. IT has been established that flotation occurs only when a finite contact angle exists between a solid and a gaseous bubble.' This angle, measured through the liquid phase, is expressed by the equation where the are inter facial free energies and the subscripts S, G, and L represent solid, gas, and liquid phases, respectively. As is seen in Eq. [I] three interface free energies, sG, sl, and GL, enter into the contact angle equation. Therefore, any variation in these energies which sufficiently varies the contact angle will, in turn, vary flotation processes. Changes made in any of the phases concerned, i.e., gas, liquid, or solid phase, are reflected through the changes occurring in two of the surface energy terms. Thus, a change in the liquid composition would be noted in sL and GL, and it is this phase, the liquid, which is most frequently altered in flotation studies., Changes in the solid phase must be reflected through the changes occurring in the sG and sL terms. In particular, it is hypothesized that changes in the surface concentrations of point defects in the solid-phase will alter the sG and sL terms which, in turn, will be reflected by flotation results. As an illustration of this hypothesis one may consider the defect structure and the flotation of AgC1. The bulk defect structure of AgCl is essentially one involving equal number of cation vacancies and interstitial cations.3 Upon adding CdC1, to AgC1, a greater number of silver ion vacancies are created in the bulk of the crystal.4 On the surface of the crystal the smaller binding forces and the free space accomodations may also allow for the creation of "surface interstitial anions", which will be designated as ad-anions. Thus, the point defect structure of the surface of AgCl doped with CdCl, will consist of cation vacancies and/or adanions. If the molecular forces responsible for the surface energies, ?SG and ?sL, are significantly altered by the presence of these surface point defects, then differences in flotation results will be noted as the concentration of these defects is varied. The defects present in AgCl are predominantly atomic in nature. In the case of PbS both electronic and atomic defects are present.5 This compound conducts electrically by either electrons or electron holes depending upon whether excess lead or excess sulfur is present. Upon disolving BiS3 in stoichio-metric PbS, one increases the concentration of cation vacancies and the number of electron carriers in the bulk of the crystal.5" At the surface, the possibility of ad-anions must also be considered. Conversely, upon dissolving AgS in stoichiometric PbS one increases the concentration of interstitial cations and the number of electronhole carriers in the bulk of the crystal.5,6' At the surface the interstitial cations will be designated as ad-cations. Thus, the point defect structure of the surface of a PbS crystal doped with Bi2S3 will consist of a number of cation vacancies and/or ad-anions and an excess of electrons. Conversely the point defects on the surface of a PbS crystal doped with Ag2S will consist of a number of ad-cations and an excess of electron holes. Again, as in the case of AgC1, should the molecular forces responsible for the magnitude of the interface free energies, ?sG and ?sL, be significantly altered by the presence of these surface defects then significant differences in flotation results will be noted as the concentration of these defects is varied. EXPERIMENTAL To test this hypothesis flotation tests were conducted on pure and doped AgCl and on PbS doped with either Bi2S3 or Ag2S. Preparation of the AgCl samples was performed as follows: AgCl and weighed amounts of CdC1, were melted in a porcelain crucible. The melt was then forced through a capillary tube and the particles emitted solidified in air as they fell about 1.5 meters. Spherical particles, -0.50 + 0.25 mm, were separated from the remaining solidified material

Jan 1, 1963

By R. E. Reed-Hill

The lattice reorientations in (1011) and (1013) twins of pure magnesium have been investigated using polarized light. Both forms (Ire subject 20 almost complete second-order twinning on the (1012) plane of the first-order twin. The observed deviations of composition planes by 6 and 3 deg, respectively, from coherent twinning planes are caused by second-order twinning. The experimental data indicate that (1011) and (1013) are reciprocal twins with a twinning shear 0.136. In a previous paper1 it was shown that the primary fracture mechanism in single crystals of magnesium strained in tension parallel to the basal plane is parting or fracture inside twins. In the temperature interval 25oto286oC, the observed twinning form, dominant in fracture, was a very small twin which formed in bands. Because these twins were very small and appeared in extensively deformed regions they did not lend themselves to X-ray analysis. Lacking Cou-ling and Pearsall&apos;s2 recently reported polarized light technique for magnesium, the twinning plane indices (K1) were originally determined by two surface composition plane measurements. This plane fell in a major zone (axis < 1120>) at an angle of 55.75 deg to the parent crystal basal plane. Because its habit deviated by 6 deg from{l0ll), 61.9 deg, the experimental data per se were not consistent with simple (1011) twinning and, for expedience, the twin was designated with habit plane indices (30341, 54.5 deg, representing the lowest set of indices corresponding to measured angles. Couling, Pashak, and sturkey3 have also found bands of reoriented lattice with a similar habit in polycrystalline specimens of magnesium and certain dilute magnesium alloys. These bands are significant because their formation in large numbers during plastic flow permit specific magnesium alloys to undergo very extensive deformation by cold rolling. Using polarized light2 they showed that the basal plane in the reoriented material was nearly parallel to the band habit and, as a result, proposed a mechanism for band formation involving a double twinning process in which (1011) twins form and then retwin according to (1012). Because of the obvious similarity between the twin bands observed in single crystals and in polycrystalline specimens, it was decided to investigate if the two phenomena were not identical and, if possible, to verify the retwinning hypothesis. The present paper is a report of this investigation and shows that the twins with the (3034) habit correspond closely to retwinned (l011) twins. Evi- dence is also given for an analogous retwinning process in (1013) twins. EXPERIMENTAL PROCEDURE Rectangular single-crystal specimen deformed in tension (stress axis in the basal plane parallel to [1010], as previously described,4 were polished electrolytically by Jacquet&apos;s method5 and etched in acetic picral.2 All twins studied in this investigation belong to a major zone, whose axis, [1210], was perpendicular to both stress axis and two sides of each specimen [(1210) surfaces]. These latter contain the plane of shear of the twins and measurements of the basal plane trace of twins on these surfaces determines the lattice orientations of the twins. The position of the basal plane in each case was determined with a polarizing microscope using a modification of the technique of Couling and Pearsall.2 For each twin the four positions of maximum extinction were measured, the data averaged, and then the pair of extinctions corresponding to the basal plane was determined by rotating the microscope stage and observing the position at which the color changed from orange to blue with a gypsum red, first-order plate inserted between the crossed Nicol prisms. EXPERIMENTAL RESULTS (1013) Twins—In general, especially in speci-mens deformed at 150°C, (1073) twins appear in greater numbers and larger sizes than (1011) twins, and the lattice reorientation inside these twins is therefore easier to study and measure. Fig. 1 shows an area of an unetched and unpolished (1210) crystal surface containing a number of (1073) twins sloping upward to the right at about 29 deg with the basal plane of the original crystal (horizontal direction). Slip line segments may be seen in both the parent crystal (running horizontally) and in the twins (sloping downward to the right at approximately -22 deg with the horizontal). As may be seen in Fig. 2, the slip lines in the twin are not at the proper angle (64 deg from basal plane of the

Jan 1, 1961

By V. T. Stringfield, H. H. Cooper

ONE of the earliest investigations of ground water in Florida was made in 1513 when Ponce de Leon arrived at St. Augustine in search of the Fountain of Youth. The history of the development of the water resources of the State shows that the large artesian reservoir that underlies Florida was discovered in the latter part of the last century. Part of that history is given by L. C. Johnson&apos; who states that the first successful artesian well in Florida was drilled at St. Augustine between 1880 and 1882. After the City of Jacksonville failed to obtain a flow of artesian water at a depth of nearly 400 ft and abandoned the drilling, R. N. Ellis, City Engineer, and L. C. Johnson, using Johnson&apos;s knowledge of the geologic structure of the artesian reservoir, estimated correctly that artesian water could be obtained at a depth of about 500 ft. Thus began the development of the large artesian system in the northeastern part of the State. In 1908, the Florida Geological Survey issued its first report on the ground water of central Florida. More recent reports give the results of investigations that have been in progress in cooperation between the Florida Geological Survey and the U. S. Geological Survey since 1930. As a result, the ground-water geology and hydrology of Florida are now so well known that ground-water problems such as confronted early investigators no longer exist. However, new problems arise and new discoveries are made as the demand for more ground water increases with the development of the State. Water-Bearing Formations Descriptions of the geologic formations and a map showing their distribution at the surface are given in a recent report by Cooke.&apos; The geologic formations that yield the ground-water supplies in Florida represent only a small part (about 1000 ft) of the total thickness of the sedimentary rocks (more than 15,000 ft) that underlie Florida. The water-bearing rocks that yield fresh water include more than two dozen formations that range in age from Eocene to recent. The Eocene formations, which consist chiefly of limestone, are the oldest and the deepest of the formations in Florida that yield fresh water to wells. In 1944, on the basis of a study of the foraminifera, the Applins -ivided the limestone of Eocene age into six formations, which are as follows, from top to bottom: Age or group Formation Jackson Ocala limestone icAvon Park limestone Claiborne -j Tallahassee limestone aLake City limestone Wilcox Salt Mountain limestone xOldsmar limestone The Ocala limestone and the underlying formations of Claiborne age, along with some of the overlying limestone of Oligocene and Miocene age, constitute the principal source of water in Florida and southeastern Georgia and generally may be regarded as forming one artesian aquifer or water-bearing unit. This aquifer is referred to in this paper as the Floridan aquifer, a name proposed by Parker.&apos; In part of Seminole County alone more than 1000 flowing wells yield water from the Floridan aquifer. A yield of 6500 gpm, or about 9.5 million gal per day, by natural flow from a well penetrating the aquifer at Jacksonville, Florida, was observed in 1942. A yield of about 7000 gpm by natural flow was reported for a well 1390 ft deep at St. Augustine in 1887. The largest yield reported from a pumped well penetrating the aquifer is 7500 gpm, or about 10.5 million gal per day. The aquifer is also the source of some of the large springs, such as Silver Springs, whose discharge, according to measurements made by the U. S. Geological Survey, has ranged from 526 to 1350 sec-ft, or from 340 to 872 million gal per day. The top of the Ocala limestone, as represented by contours in Fig. 1, indicates in a general way the geologic structure of the formations that comprise the Floridan aquifer. The Ocala is at or near the surface in the areas represented by shading in the northwestern part of the peninsula and also in an area in western Florida adjacent to Alabama and

Jan 1, 1952

By R. H. Frazier, C. H. Lorig, F. W. Boulger

This investigation establishes the effect of ferrite grain size resulting from various heat treatments on the transition temperature of a semikilled steel plate. Different austenitizing temperatures and various cooling rates were used. The ductile-brittle transition temperatures were determined by the Navy tear test and the keyhole Charpy test. THE data presented in this paper deal with quality characteristics of ship-plate material which were investigated in a research project sponsored at Battelle by the Bureau of Ships, Dept. of the Navy. Specifically, the object of this investigation was to establish the effect of ferritic grain size (resulting from various heat treatments) on the so-called transition temperature of ship-plate steel. Transition temperature is not a fixed property of steel. It is derived from a series of static or dynamic tests made at various temperatures and is qualified by specifying the type of test employed as well as the testing criteria. Because in earlier investigations of ship-plate quality1,2 the so-called Navy tear test and standard notched-bar tests (keyhole Charpy) proved to be useful in interpreting instances of brittle behavior of ship plate in service, these tests were used in the investigation reported in this paper. By definition,&apos; in the Navy tear tests the highest temperature at which one or more of four specimens breaks with a brittle fracture (that is, when less than 50 pct of the fracture area has a dull fibrous texture) is termed "transition" temperature. In the Charpy tests, the 12 ft-lb level of energy absorption was used as a criterion indicating the "transition" temperature, although other levels of energy absorption were also used for comparison. Earlier work" on ship-plate steels indicated that the temperature at which ship plate is finished has a very significant effect on its notched-bar properties. Plates rolled in the laboratory, where the finishing temperature can be carefully controlled, showed a 16°F decrease in tear test transition temperature when the finishing temperature was lowered 200°F (from X" to Y°F). The same plates showed a drop of 10°F in the keyhole Charpy transition temperature from the same decrease in finishing temperature. Commercially finished plates&apos; exhibit a similar trend. When the ferrite grain size of the hot-rolled laboratory plates was determined, a close relationship was found between the ferrite grain size and the notched-bar transition temperature." " he indicated relationship between grain size and transition temperature was in agreement with the findings on low carbon steels of Hodge, Manning, and Reichhold&apos; despite the differences in composition of the steels. The cooling rate after rolling varies from one steel plant to another. This variation changes the micro-structure" and appears very likely to affect the notched-bar properties of the steel plates. In the investigation summarized in the present paper, heat treatments simulating finishing practices in the hot rolling of ship plate were used in order to vary the ferritic grain size. It is believed that the indicated relationship between grain size and transition temperatures of the ship-plate material will prove useful in estimating the effect of rolling temperature and of cooling rates from rolling temperatures on the notched-bar properties of semikilled steel plate. Material The semikilled steel plate used in this investigation was a ¾ in. hot-rolled plate from an open hearth heat. Other plates from this heat have been used on many other studies performed for the Ship Structure Committee," "," and the heat has been identified as project steel "A". The chemical composition of the plate1 was 0.25 pct C, 0.49 pct Mn, 0.011 pct P, 0.045 pct S, 0.04 pct Si, and 0.004 pct N.

Jan 1, 1956

By Richard G. Warren, Michael M. Minor, Gayle J. Thomas

INTRODUCTION Los Alamos Scientific Laboratory (LASL) initiated its effort in the Hydrogeochemical and Stream Sediment Reconnaissance (HSSR), a part of the Department of Energy (DOE) National Uranium Resource Evaluation (NURE) program, in late 1975. Since that time, LASL has completed sampling of the Rocky Mountain states of New Mexico, Colorado, Wyoming, and Montana at a density of about one water or waterborne sediment sample per 10 km2 and has sampled about 85% of Alaska at a density of at least one per 25 km2. Analytical results for these samples are reported by National Topographic Map Series (NTMS) quadrangle. All collection and analytical procedures have been standardized from the outset (Sharp, 1977; Sharp and Aamodt, 1978). Until early 1979, only uranium results were reported for these samples; thereafter, results include analyses for at least 42 additional elements in the sediment samples. Each LASL HSSR report also includes a discussion of the relationship of these analytical data to known or possible uranium resources; more recently, these data have been re- examined for their relationship to resources for other metals (Beyth et al., 1980; 1980a). Analytical results for LASL HSSR sediment samples are both comprehensive, including 43 elements, and precise, allowing close inter-comparison of data between quadrangles. A recent HSSR study shows that elemental concentrations in sediment samples from the Dixon Entrance quadrangle in Alaska are insensitive to the choice of sieve size fraction and do not vary significantly between stream locations a few meters apart, except for extremely high elemental concentrations (Warren, et al., 1980). Elements that are particularly reproducible include thorium, hafnium, and the .ram earth elements. Fortunately, sensitivities for these elements, which are often associated with uranium, are excellent by the nondestructive analytical technique of neutron activation analysis that LASL employs. Wet chemical techniques may not always give reliable results for these elements in sediment samples due to the difficulty of dissolving the resistate mineral phases that normally contain these elements. LASL has recently open-filed results for a large number of NTK3 quadrangles; to date analyses have been reported for about 605 of the quadrangles within the states of the Rocky Mountain region. As a result, uranium analyses am now complete for all sediment samples collected from the state of Wyoming. We have chosen to sumnarize the analytical results for Wyoming and portions of adjoining states hereafter termed "the ~ Wyoming regionn (Fig. 1 ) ; nearly 24 000 uranium analyses and nearly 17 000 analyses for 42 additional elements are available for sediment samples collected from this area. The DOE open-file report numbers are shown in Fig. 1 for reports open filed before September 1, 1980. The Wyoming region provides an ideal area for an examination of regional geochemical patterns ex- hibited by sediment samples. It is endowed with a variety of exposed geologic units and with widely distributed uranium districts associated with host units of several ages. However, discussion will focus on rock units of Eocene and Precambrian ages because they are widely exposed and host the majority of the uranium resources within the region (Fig. 2). Miocene units are also widespread and host mineralization in the Brown&apos;s Park Formation (Fig. 2). Epigenetic uranium mineralization occurs in sand- stones of lower Eocene age such as the Wasatch, Battle Springs, and Wind River Formations whereas vein type mineralization occurs in Precambrian crystalline rocks. Precambrian rocks within the region consist of a variety of granitic and meta- morphic rocks with l .4-2.8 billion year ages, except within the Uinta Arch, where they consist of a sequence of very low grade metamorphosed or unmetamorphosed 1.0 billion year old sedimentary rocks. Precambrian rocks have served as sources for much of the clastic material comprising the lower Eocene units, and may also have provided the source for the uranium in mineralized Eocene or Miocene sandstones (Stuckless, 1979). The remainder of this paper describes the relationship of elemental concentrations in HSSR sediment samples to exposures of Eocene and Precambrian rocks. The results are used primarily to determine where these Precambrian rocks might provide the most suitable uranium source areas and to infer the direction of transport toward adjacent depositional basins during the Eocene.

Jan 1, 1980

By O. R. Morris, G. L. Hawkes

A galvanic cell, using as electrolyte a fused salt solution of calcium carbide and as electrodes carbon and a Fe-C alloy of known composition, has been set up to study the thermodynamics of Fe-C alloys in the temperature rmzge 800" to 1000°C. Time independence and reproducibility of the cell electromotive force were taken as evidence of the reversible behavior of the cell. Carbon was believed to be present in the electrolyte as the so-called acetylide ion, C;-. The plots of the cell electromotive force us temperature for a specific alloy composition were straight lines within the limits of experimental error. The average Partial molar enthalpy of carbon in iron relative to pure carbon was found to be +10,610 i 93 cal per g-atom C. Thermodynamic analysis of the data has led to the following equation for the carbon activity, ac, based upon pure carbon as the standard state: In ac = In Zc + 10,560/RT + (10.02 + 77O/T)ZC - 2.350 where ZC is the lattice ratio [nC/(nF, - nc )] and T is the absolute temperature. This equalion gives carbon activity values generally slightly lower than those from gas equilibration studies reported in the literature. METAL LOGRAPHIC examination of a polished cross section of the steel anode used in the electrolysis studies of fused salt solutions of calcium carbide by Morris and Harry revealed extensive carburization of the steel by the electrodeposited carbon. This carburization was reflected in the variability, with time, of the applied potential to the electrolysis cell, necessary to maintain a constant current density at the electrodes. This observation suggested the setting up of a galvanic cell of the "alloy concentration" type to study the thermodynamics of some metal-carbon alloys. Cells of this general type have been widely used for the study of alloy systems.2 In view of the availability of published data in respect of the austenite phase of the Fe-C system, it was decided to carry out measurements upon these alloys before proceeding to studies of less well documented systems. The galvanic cell may be written: where [C] is carbon dissolved in iron. The electrolyte was a fused salt solution of calcium carbide, containing some 5 to 10 mol pct of carbide. The cell reaction is believed to be: C(s)-[CI [I1 Carbon forms an interstitial solid solution in iron, with the atoms located in the octahedral interstices. In the fcc crystal structure of austenite there is one octahedral interstice per iron atom. Thus, the lattice ratio, ZC, shown by Gurney3 to be the fundamental concentration parameter in the context of interstitial solutions, is given by: where nc and nFe are the number of carbon and iron atoms, respectively. chipman4 has recently shown empirically the advantages of using this concentration parameter instead of the more usual atom ratio or atom fraction. The cell electromotive force, E, assuming reversible behavior, is related to the carbon potential or the partial molar free energy of carbon in the solid solution relative to pure carbon at the same temperature and pressure, GP at the composition ZC, by the equation: where z is the carbide ion valency and F is the Faraday constant. An activity of carbon, ac, in the solution relative to the value of unity assigned to pure carbon, and an activity coefficient, qC , are defined such that: where R is the gas constant and T the absolute temperature. GF is further related to the relative partial molar enthalpy Hm, and the temperature coefficient of the cell electromotive force, (aE/aT)Zc, by the equations: Measurement of the cell electromotive force thus enables calculation of the relative partial molar thermodynamic properties of carbon in iron, if z is known. At E = 0, the solid solution is in equilibrium with pure carbon. More convenient for many purposes is the standard state based upon the infinitely dilute solution, Henry&apos;s law. The relationship between the activity coefficient of carbon based upon this standard state, and that based upon the pure carbon standard state, qC , may be obtained by considering the free energy of transfer of carbon from the latter standard state to the former. The relationship is: where +:H is the activity coefficient of carbon in the hypothetical standard state based on a reference of

Jan 1, 1969

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult&apos;s law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and&apos; oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1&apos;2 The PbO-SiO2 melts are ionic conductors.&apos; During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By G. L. F. Powell, L. M. Hogan

Large degrees of undercooling have been produced in bulk samples, 400 g, of copper and Cu-O alloys by melting in a slag of commercial soda-lime glass. The maximum degrees of undercooling obtained for copper, hypoeutectic and hypereutectic Cu-O alloy samples were 208°, 218°, and 97°C, respectively. No grain refinement as a function of undercooling was observed for the pure copper samples although in Cu-O alloys there was a marked decrease in grain size at degrees of undercooling greater than 150°C. The grain size change is the result of recrystallization during or immediately following the freezing process. THE first report of a large degree of undercooling in a bulk sample of metal was that by Bardenheuer and Bleckmann1 who produced 258°C undercooling in a 150-g sample of iron by melting in a glass slag. Garbeck2 extended this technique to nickel, cobalt, and copper and reported maximum undercoolings of 220°, 230°, and 60°C, respectively, while Fehling and schei13 undercooled a large number of metals as 2 to 20-g samples slagged in glass. Subsequently, one of the authors4 applied the glass slag technique to bulk samples, -500 g, of silver and obtained a maximum undercooling of 250°C. It was concluded that impurities which normally catalyze nucleation at small degrees of undercooling could be removed by oxidation and solution in a glass slag. Large undercooling of bulk samples of iron, nickel, cobalt, and their alloys has also been reported by other authors.8&apos;10&apos;11 Of the five metals mentioned above, copper was the only one which had not been undercooled by at least 200°C in the form of a large bulk sample. Since copper exhibits high liquid solubility for oxygen, as do iron, nickel, cobalt, and silver, it was considered that a much larger degree of undercooling than that observed by Garbeck for copper should be possible. This was obtained by modification of the technique applied previously to silver and the results of undercooling experiments with 400-g samples of copper form part of this paper. The undercooling behavior of Cu-O alloys was also studied, and the influence of a small oxygen content on the grain structure of undercooled copper was observed metallographically. 1) EXPERIMENTAL The copper was obtained as oxygen-free high-conductivity copper, the major impurities of which were Fe 0.01 pct, Zn 0.015 pct, and Si 0.02 pct. Melting was carried out in an open-ended vertical cylindrical fur- nace wound with Kanthal wire. A schematic diagram of the experimental setup is shown in Fig. 1. The undercooling technique previously used for silver4 involved preoxidation of the samples by melting the silver in contact with the atmosphere. The oxygen content was subsequently reduced by freezing the samples under a glass slag, whereby the oxygen was evolved as gas and the continuous glass cover over the surface prevented re-solution of oxygen when the sample was remelted. Since oxygen is not released as gas when a Cu-O alloy is frozen. the technique had to be modified for use with copper. Also, copper is oxidized during fire refining so that an in situ preoxidation treatment of the samples was not considered to be a prerequisite to large undercooling. Experimentation proved that this supposition was correct. Instead, it was found that care was necessary during melting of the copper under glass to minimize oxygen pickup. Samples of copper weighing 400 g were prepared by adding 50-g pieces of copper to a vitreous silica crucible partly filled with soda lime glass at a temperature of approximately 1000°C. Each piece was quickly immersed in the glass slag and held at this temperature until the oxide coating on the surface decomposed. This change was easily observed and coincided with the formation of gas bubbles in the glass

Jan 1, 1969

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 D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.&apos; and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~&apos; have reported the structure of

Jan 1, 1965

By P. G. Shewmon

A novel technique for determining the surface energy (?) and its derivative with respect to orientation, (?&apos;) is described. Essentially it involves the &apos;floating" of a wedge on the substrate, said wedge being made of a material which is not wet or only slightly wet by the substrate, i. e., as a greased needle "floats" on water. A thermodynamic analysis of a system in which the wedge is supported entirely by surface energy is given. If the original suyface is not at a cusp orientation, the surface tension is directly measurable from the groove angle formed. If the original surface is at a cusp orientation, there may or may not be a groove depending on the relative value of ?&apos; and the weight of the wedge. Experiments primarily on copper and silver showed that sapphire, quartz and refractory metal wedges were wet while graphite wedges were not. The technique was demonstrated to work using graphite wedges, but the results obtained were not as eccurate as those obtained by other workers using the wire-creep experiments. It is concluded that the technique might prove most useful with non-metals where ?&apos; is large and filament creep experiments would be quite difficult. If an absolute value of the surface free energy (?) of a metal is to be determined, the most reliable methods used to date measure an average over the various orientations exposed on a polycrystalline sample. For example, ? for silver, gold, and copper have been measured by determining the force required to just keep a thin wire,&apos; or foil,&apos; specimen from contracting under the influence of ?. Herring 3 has predicted and experiment confirms, that the sensitivity of this method is inversely proportional to the grain size.&apos; Thus it cannot be used to measure ? for a particular orientation by using a foil single crystal or a very coarse-grained specimen. An accurate value if ? for tungsten averaged over a range of orientations has been determined using a field emission technique. The same techniques cannot or have not been used to measure ? for non-metallic solids, and as a result the values available are much less accurate.4 This Paper resents a means of making an absolute determination of ? for a particular surface orientation on any solid, as long as the given surface orientation does not break up into other orientations during an anneal. Experimentally ? is found to vary with orientation and at a few low index orientations it is found to have a cusped minimum, i.e., the derivative of ? with respect to the orientation of the surface changes discontinuously at the low index orientation, see Fig. 1. The slope of a plot of ? vs orientation (herein designated ?&apos;) is called the torque on the surface, since it tends to rotate the exposed surface toward the low index orientation, or if the surface is at the cusp orientation it opposes any force tending to rotate the surface out of the low index orientation. The ratio ?&apos;/? has been determined for a few metals, but in cases where this ratio is high there is presently no means of determining either ?&apos;/? or the absolute value of ?&apos; for the orientations present on an annealed surface. The technique discussed herein also provides a means of determining an absolute value of ?&apos; for those orientations which deviate only infinitesimally from a cusp orientation. It should work best on surfaces where ?&apos;/? is large; that is, for cases where no other technique is available for measuring ?&apos;. Aside from trying to learn more about surfaces through measuring ? and ?&apos;, the primary reason for wanting values of ? or ?&apos; is to study adsorption. From measurements of the variation of ? for a particular orientation with the concentration of an impurity, one can obtain the number of impurity atoms adsorbed per unit area (Ti) on that orientation using the Gibbs adsorption equation.&apos; where µi is the chemical potential of the adsorbed impurity. Thus, if absolute values of ? could be obtained for the free surface of a given surface orientation as a function of µi, ri could be determined for the given orientation. Furthermore, by equilibrating a grain boundary with the given surface at various values of ki, one could also determine ri for the grain boundary. Similarly Robertson 6 has pointed out that if y is taken to be a continuous function of and µi, then a2 ?/a @a µ2 = a2 ?/a pi a +. Thus, at all orientations away from cusps the following equation holds From a measurement of ?&apos; vs ki, it is thus possible

Jan 1, 1963

By R. W. Hyde, B. S. Old, S. E. Eaton

INTRODUCTION ONE of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects on both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steelmaking. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2.1 The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2,3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. Still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States, It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaSO4), The sulphur is subsequently found in the coke in combination with carbonaceous material of unknown composition and as calcium and iron sulphides: In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke, Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two major forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high in total sulphur, would yield coke of fairly low sulphur content, Using the new

Jan 1, 1948

By Kenric C. Owen

INTRODUCTION Situated 23 miles east of Pretoria the Premier Mine started diamond production in 1903. Two years later it produced the largest diamond yet discovered, the 3 106 carat Cullinan stone. For the period to 1932 when the mine was closed down due to economic circumstances, open cast mining was practised using inclined rope haulage traction and by this time had produced 48.5 million carats of predominantly industrial quality diamonds from 148 million tons of ore. In 1945 it was decided to re-open the mine using underground mining methods. A system using long hole benching was devised (Hodgson and Sewel 1960). This system was later modified but still forms the basis for approximately fifty percent of production. Following the successful introduction of block caving on associated diamond mines in the Kimberley area (Gallagher and Loftus 1960) this mining method was introduced to the Premier Mine in the late 60&apos;s and now accounts for nearly 50% of production. This paper will discuss block caving at Premier Mine in the light of our experience and discussion will be directed to the main geological and structural features of the orebody and host rocks and the related constraints imposed on the mining methods. Reference is made to the long hole benching mining method for comparative purposes. GENERAL DESCRIPTION OF OPERATIONS The ore from the block caving and bench mining areas gravitates via ore passes to a twin haulage, 500m below surface. Electric 13 tonne locomotives, each hauling a train of 10 Granby type cars, deliver the ore to two 42" x 48" (1.06m x 1.22m) jaw crushers. The ore is reduced in size to minus 0.15m before being hoisted to the treatment plant on surface. Hoisting is done with 12.5 tonne bottom discharge skips in a five compartment rectangular shaft using two 3 240 H.P. semi automatic Ward Leonard winders. A small single drum service winder operates in the other compartment. Men and materials travel in a separate shaft in a 5,4m x 2,8m cage operated by a Koepi winder. These two shafts are also the main intake airways to the mine. The two main extraction fans capable of 250 m3/s at 3,2 kPa are situated on surface and are connected to the underground workings by an incline and a network of air passes and return airways. GEOLOGY Although there are numerous occurrences of kimberlite bodies in the district, the Premier Mine kimberlite pipe is the only economic orebody. It is roughly oval in shape with surface dimensions of 900m on the long axis and 450monthe short axis. The surface area is 320 000 m2. The kimberlite has intruded a massive body of felsite and norite which is intersected by a number of faults. The contact between the kimberlite and host rock is clear cut and dips inward at an average angle of 80°. Cutting across the pipe and the country rock is a 75 metre thick gabbro sill, the top of which intersects the pipe below the 347m level and dips at 15&apos; to the north west. The kimberlite has been metamorphosed a distance of some 20m both above and below the sill contacts. Age measurements on biotite from the gabbro date the sill as 1 115 million years, thereby providing a minimum age of the pipe. (Pre Cambrian). All other pipes in South Africa are of Cretaceous age (60 million years). A simplified geological plan and section of the Premier Mine orebody is shown in Figure 1. It is thought that the kimberlite intruded in at least three distinct phases. The kimberlites of these different phases can be distinguished most easily by their characteristic colour. BROWN KIMBERLITE. This is the oldest kimberlite and forms a crescent shape in plan on the south eastern side of the pipe. In depth it increases in relative area. Although the brown kimberlite carries the highest diamond grade in terms of carats per ton all the various kimberlites in the Premier pipe are economic to mine.

Jan 1, 1981

By H. H. Hausner, O. V. Roman, F. V. Lenel, G. S. Ansell

The radial shrinkage during sintering of cylindrical compacts and loose aggregates of copper powder was measured. It was found to be nonuni-form from top to bottom of the samples and to depend upon the method of supporting them. The non-uniformity is due to the effect of gravity forces during sintering. Since gravity has an effect in sintering without externally applied stresses, no sharp dividing line can be drawn between conventional sintering and hot pressing. RECENT investigations of the sintering behavior of compacts1 and of loose powder aggregates2 have indicated that forces, other than those arising from surface tension effects, may play a role in shrinkage. In compacts it was shown that residual stresses from the pressing operation influence shrinkage behavior. In loose powder aggregates gravity forces due to the weight of the powder affect the ratio of shrinkage in the vertical and the horizontal direction. The main effort in the work reported here was to show that gravity plays a role also in the sintering of compacts. A few additional experiments were made confirming the effect of gravity in the sintering of loose powder aggregates. EXPERIMENTAL PROCEDURE Compacts and loose powder aggregates were prepared from irregularly shaped, electrolytic copper powder. Prior to use the powders were reduced 30 min at 400°C in dry hydrogen to remove surface oxides. Then the -325 mesh size fraction was separated from the -100 + 325 mesh fraction. The compacts were pressed at a pressure of 10,000 psi from 50 g of powder in a hardened steel die, 1 in. in diam. The height of the compacts was 0.725 i 0.005 in. An effort was made to get as uniform a green density distribution in the compacts as possible. The walls of the die were lubricated with a suspension of 3 pct of zinc stearate in acetone and the compacts were pressed using double action by first pressing the powder at 1200 psi with the die barrel supported, then removing the sup- ports and pressing to final pressure of 10,000 psi with the die barrel floating. The pressure was maintained for 10 sec. The compacts were sintered at a temperature of 925°C, generally for 1 hr. In order to maintain uniform temperature they were sintered in boats made from cylindrical copper blocks. The blocks were 2 in. in diam, either 2 or 2 1/2 in. long and, split to form the body of the boat and a lid. The body of the boat contained a cavity 1 3/8 in. wide, 1 in. deep and either 2 1/8 or 1 3/8 in. long. The longer cavity accomodated two samples, the shorter one only one sample. The uniformity of temperature distribution within the boats was checked with thermocouples welded to the top and bottom of the samples. The maximum variation between top and bottom temperatures was i 1/2°C. The actual sintering temperature was held constant within ±2°C. In order to determine the effect of gravity forces, i.e., the weight of the compacts, upon shrinkage, they were supported in the following ways during sintering: a) Full Bottom Support. The compacts rested either on a flat alundum disk or on alundum powders. b) Partial Bottom Support. The compacts rested on a graphite cylinder, 0.3 in. in diam which formed a projection on a larger graphite disk. It is difficult to balance the compact on the small projection. To avoid having the compact tip, a small hole was drilled through the compact and through the graphite disk and its projection. The graphite disk was then suspended from the lid of the boat by a thin iron wire which passed through the holes in the disk and the compact. c) Top Support, first type. A hole 3/32 in. in diam was drilled diametrically through the green compact 3/16 in. from the top of the compact. The compact was sintered suspended from an alundum rod (thermocouple protection sleeve) inserted into the hole. d) Top Support, second type. A hole was drilled axially through the center of the compact. The upper part of the hole from the top surface of the compact one fourth of the way down was 1/16 in. in diam; the lower part of the hole from the bottom surface three fourth of the way up was 3/32 in. in diam. The compact was suspended from the lid of the boat by an iron wire passing through the upper part of the hole and then tied into a knot. The loose powder aggregates were made by filling l in. deep, l in. diam cylindrical graphite molds with -325 mesh powder. To achieve uniform density in all the loose powder aggregates, the powders were settled in the molds by placing the

Jan 1, 1963

By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.&apos;.&apos; In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes&apos; upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies&apos; is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954