Search Documents

By J. P. Hammond, C. J. McHargue

The wire textures for cold rolled and recrystallized iodide titanium and the sheet textures for this material produced by cold and hot rolling, and recrystallization at a series of temperatures were determined. &apos;The effect of the a + ß transformation on the sheet texture was noted. UNTIL recently it was believed that all hexagonal close-packed metals deformed by slip on the basal plane, (0001), and that rolling should tend to rotate this slip plane into the plane of the rolled sheet. The pole figures of cold rolled magnesium&apos; are satisfactorily explained on this basis. There is a tendency for the <1120> directions to align parallel to the rolling direction, and the principal scatter is in the rolling direction. Zinc% as a rolling texture in which the hexagonal axis is inclined 20" to 25" toward the rolling direction. Twinning is believed to account for the moving of the basal plane away from parallelism with the rolling plane. The texture of beryllium3 places the basal plane parallel to the rolling plane with the [1010] direction parallel to the rolling direction, and the scatter from this orientation is primarily in the transverse direction. Cold rolled textures reported for zirconium&apos; and titanium5 how the [1010] directions to lie parallel to the rolling direction and the (0001) plane tilted by approximately 25" to 30" to the rolling plane in the transverse direction. Rosi has recently reported that the mechanisms for deformation in titanium are distinctly different from those commonly reported for hexagonal close-packed metals. The principal slip plane is the prismatic plane, {1010), with some slip also occurring on the pyramidal planes, (1011). However, there is no evidence for basal slip. The slip direction is reported to be the close-packed digonal axis, [1120]. In addition to the twin plane commonly reported for metals of this class, {1012), Rosi found the twin planes (1122) and {1121), with the dominant twin plane being (1121). Information regarding the recrystallization and hot rolling textures of hexagonal close-packed metals is limited. Barrett and Smigelskas report that rolling beryllium at temperatures up to 800°C and recrystallization at 700°C produce textures not differing from the cold rolled sheet texture.3 McGeary and Lustman find that hot rolling at 850°C produces the same basic texture in zirconium as rolling at room temperature.&apos; These investigators also report that the texture for sheet zirconium recrystallized at 650 °C differs from the cold rolled orientation inasmuch as the [1120] direction, instead of the [1010] direction, is parallel to the rolling direction. In the case of titanium, it is not possible to deduce which direction is preferred in the recrystallized state from the pole figures presented by Clark." The purpose of this paper is to report an extensive investigation of the preferred orientations in iodide titanium. Since the deformation mechanisms for titanium are different from those commonly given for hexagonal close-packed metals, it is not surprising to find distinct differences between the textures of titanium and other metals of this class. Materials and Methods This investigation was carried out on iodide titanium obtained from the New Jersey Zinc Co. with an analysis as follows: N2, 0.002 pct; Mn, 0.004; Fe, 0.0065; A1, 0.0065; Pb, 0.0025; Cu, 0.01; Sn, 0.002; and Ti, remainder. The crystallities of titanium were broken from the as-deposited bar and melted to form 20 g buttons on a water-cooled copper block in a vacuum arc-furnace. Hardness tests conducted on the material before and after melting differed by only two or three Vickers Pyramid Numbers, indicating no or insignificant contamination. The buttons were hot forged, ground, and etched to sizes and shapes suitable for the rolling schedule, and vacuum annealed at 1300°F. Specimens for determination of the wire textures were reduced 91 pct in diameter to 0.027 in. in 24 steps using grooved rolls. In order for the orientation of the central region to be studied, portions of these wires were electrolytically reduced to a diameter of 0.005 in. using the procedure described by Sutcliffe and Reynolds.&apos; The sheet textures were determined on titanium cold rolled 97 pct to a thickness of 0.005 in. A reduction of approximately 10 pct per pass was used, and the rolling direction was changed 180" after each pass. Specimens used for determination of the recrystallized textures were annealed in evacuated quartz tubes at 1000°, 1300°, and 1500°F. The grain size of the 1000°F specimen was sufficiently small to give satisfactory X-ray patterns with the specimen stationary. However, it was necessary to scan the surface of the other recrystallized specimens. The microstructure of each annealed specimen was that of a recrystallized material. The diffraction rings all showed the break-up into spots typical of recrystallized structures.

Jan 1, 1954

By J. J. Pye, J. B. Drew

Mzasurements of the surface diffusion coefficients of metals have been made. Diffusion profiles for the Ag-Ag system were obtained by means of a radioactive point source and a precision auto-radiographic technique. The activation energy for silver self diffusion (=8.1 kcal per mole) is lower than that previously reported (-10 kcal per mole) on poly crystalline wire by Nickerson and Parker. The bresent data indicate an effect due to parasitic volume diffusion at temperatures above 500°C. RELATIVELY few measurements have been made of the surface self-diffusion coefficients of metals. Nickerson and arker&apos; measured the diffusion of silver over the surface of poly crystalline wires and estimated that the activation energy was 10.3 kcal per mole. Winegard and chalmers2 carried out measurements on both polycrystalline and single crystal surfaces but did not report a value of the activation energy. They found, however, that at temperatures between 250" and 400°C the diffusion coefficients were on the order of lo-&apos; sq cm per sec and that there was an acceleration of the migration of silver on the polycrystalline sample when a change of surface shape occurred. Winegard and Chalmers used an autoradiographic technique, hereafter designated ARG, and Nickerson and Parker used a surface scanning geiger counter in order to determine the diffusion profiles. More recently, Hackerman and simpson3 measured the surface self-diffusion coefficient of copper at a single temperature (750°C), and the value of the diffusivity (- 10-5 sq cm per sec) is in agreement with that given by jostein from his thermal grooving measurements. This paper reports the results of an investigation of the surface self-diffusion coefficients of silver over a large temperature range and describes the adaptation of autoradiographic (ARG) techniques for the determination of diffusion profiles obtained from a radioactive point source. EXPERIMENTAL PROCEDURE The experimental procedure is a modification of the method employed by Hackerman and simpson3 in their measurements on copper. A brief description of their technique is as follows: A radioactive needle which sinters to the surface during the diffusion an- neal serves as the source of diffusing atoms. After the diffusion run the needle is removed and the surface is scanned with a shielded counting arrangement. The diffusion profiles reported in this paper were obtained by a modification of the above procedure which employs a precision ARG technique. Previous investigations in this laboratory and elsewhere51B have shown that under carefully controlled developing conditions and by the use of calibration sources a linear relation exists between the concentration of the isotope and the photographic density for values below unity. The use of ARG under these conditions has advantages over the counter scanning method in that cumbersome shielding and requirements for great mechanical precision of the scanner are eliminated. Also the ARG gives a complete picture of the surface which is advantageous in studies of anisotropic diffusion. A recording microdensitometer having a 0.1 p wide slit was employed. At low temperatures the disturbing effects of subsurface radiations are negligible. The diffusion anneals are carried out in the cell shown in Fig. 1. The needle is formed by grinding down a 1.0 mm rod of high-purity silver until a tip of 0.2 mm radius or smaller is formed. This tip is plated withA"&apos; which becomes the source of the diffusing atoms that are detected by ARG. The needle carrier and the crystal holder, Fig. 1 are constructed of quartz and ports are provided in the holder pedestal which allow free vapor circulation ((2.0 oz) and the carrier apron fits snugly over the crystal holder cap, insuring that the needle does not move and scratch the surface. Temperatures are provided by a stabilized tubular furnace which can be quickly positioned around the cell, thus bringing the crystal up to temperature in a time that is short compared to the diffusing times. The diffusion anneals range from 2 hr for the high-temperature samples to about 25 hr for those at the lowest temperature. The possibility of vapor transport of the radioactive metal as a contributing factor in the diffusion profile was investigated in two ways. One method was to suspend the needle directly over a dummy sample, raise the temperature, for periods of time equal to the diffusion times, and then take an auto-radiograph of the surface. Negligible radioactivity appeared. In the second method a thin slot in the crystal face on one side of the source provided a "cong path" for surface diffusion. If evaporation was the primary source of surface atoms the region of radioactivity around the source would be symmetrical. This was not the case. The profile dipped abruptly at the edge of the slot but on the other side of the source the usual diffusion profile appeared.

Jan 1, 1963

By T. S. Lovering

GEOCHEMICAL prospecting extends the age-old method of searching out lodes with a gold pan and rationalizes the prospector&apos;s hunch that certain plants are associated with ore. It uses sensitive but cheap and rapid analytical methods to find the diagnostic chemical variations related to hidden mineral deposits. Exploration geologists can gain tremendous assistance from this new tool, although its optimum use is not simple. To bring out the geochemical pattern that reveals the presence of a hidden ore deposit with a minimum number of samples requires a combination of shrewdness, chemical knowledge, and exploration geology. The use of sensitive analytical methods for prospecting had its start in the 1930&apos;s in northern Europe, where Scandinavian and Russian geologists had some success in these early efforts. Very little geochemical prospecting was carried on in the United States at this time, and no sustained interest was manifest until the close of World War 11, when geochemical investigations were started by the Mineral Deposits Branch of the U. S. Geological Survey. The purpose of these investigations was to apply geochemical principles and techniques to surface exploration for mineral deposits. Both the research on analytical methods and the routine trace analyses for field investigations were at first conducted by a single group, but it later became apparent that the trace analyses could be done by men of less experience than that required for successful research on methods. For the past several years there have been two groups of chemists, and although their functions overlap, three of the chemists are chiefly concerned with research, while four to six other men make the trace analyses for field projects. The chemical investigations, as well as the field projects of the Geochemical Exploration Section, concern only those phases of the subject that are appropriate to a government organization; every effort is made to help private industry, but not to compete with it, in finding orebodies. The chief aim of the Section, therefore, is to develop new analytical techniques and publish the results promptly, to carry out field investigations of the fundamental principles of geochemical dispersion, and to field test promising- techniques under controlled conditions. Some routine geochemical exploration work is carried on in connection with DMEA loans, and in district studies where the project chief wishes geochemical information on certain areas for his report. It should be emphasized, however, that geologists of the Geochemical Exploration Section are primarily concerned with fundamental principles underlying the distribution, migration, and concentration of elements in the earth&apos;s crust. To facilitate the use of geochemical methods the USGS has published much information on its methods of analysis and has provided opportunities from time to time for qualified professional personnel to study these methods, to work in the USGS laboratory, or to attend demonstrations of the analytical techniques at the Denver Federal Center. Typical of the research carried on are the problems now being investigated: 1) Development of rapid and sensitive analytical methods suitable to the determination of traces of metals and other minor elements in various materials, such as rock, soils, plants, and water. At the present time attention is being concentrated on U, Bi, Cr, and Hg, and satisfactory rapid trace analytical methods are virtually perfected for U and Bi. Good methods are also available for: Cu, Zn, Pb, Ni, Co, As, Sb, W, Mo, Ag, Nb, Ge, V, Ti, Fe, Mn, S, and P. 2) The relation of geochemical anomalies in plant materials to the geochemical distribution of elements in soils surrounding the plant. 3) A study of the dispersion halos in transported sedimentary cover such as glacial drift and alluvium over known orebodies. 4) A study of the behavior of ore metals in the weathering cycle. 5) A study of the behavior of the ore metals during magmatic differentiation. This requires a study of the distribution of minor metals in fresh igneous rocks and their component minerals in a well established differentiation series and in adjacent country rock. 6) A study of the dispersion of metals in primary halos in the wall rock surrounding orebodies. 7) Regional and local studies of the metal content of surface and groundwater in mineralized and barren areas. Many field projects of the Mineral Deposits Branch also require the services of USGS chemists during their investigation of the geochemical environment of ore deposits. From the work that has been done certain general principles have emerged. Concentrations of an element that are above the general or background value of barren material are called positive geochemical anomalies or simply an anomaly, whereas values less than background are called negative anomalies. The anomalies most commonly investigated in geochemical prospecting are those formed at the earth&apos;s surface by agents of weathering, erosion, or surficial transportation, but more and more attention is being given to primary anomalies found

Jan 1, 1956

By H. Sigurdson, C. H. Moore

Extensive studies have been carried out on electric furnace and blast furnace slags obtained in the winning of iron from its ores. These slags normally consist of elements of the gangue minerals present in the ores, as well as the added flux materials. In consequence, melts of CaO, MgO, Al2O3 and SiO2 can be considered as representing typical slag compositions. When a slag of this composition cools, it usually crystallizes according to predictions possible from an equilibrium diagram of these constituents, providing the melt is not undercooled to form glass. The melt is either viscous or fluid, depending upon the ratio of binary cations to silica, and crystallizes easily or forms a glass for the same reasons. If the melt is not overheated so that carbides of the metal components of the slag are formed and if the composition of the slag is so adjusted that it has a high fluidity, liquid equilibrium is attained and the slag can be held in a liquid state for extended periods of time. Upon tapping, the slag crystallizes into minerals, the type and proportion of which are determined by the melt composition. Since equilibrium is attained, the holding period is not critical. In melts containing a large increment of titanium, however, the normal slag procedures are not applicable. Titanium, as one of the atomic transition elements, is, at elevated temperatures, capable of being reduced to form metalloid compounds much more readily than the refractory oxides present in normal slags. In consequence, an oxide melt containing titanium never reaches equilibrium in a reducing environment, but continues to shift its composition until cooled. If melts of this nature are cooled and samples submitted to metal-lographic and X ray analysis the course of reaction and crystallization in this type of slag can be determined. Preparation of Slag The slags investigated fell into the system CaO-MgO-TiO2-Al2O3-SiO2 and were produced from ilmenite ores reduced by carbon in an electric furnace. Since the equilibrium series1 and the laboratory smelting of ilmenite2 are described in two of the accompanying papers, detailed description of the smelting procedure is not required here. However, certain essentials must be mentioned. Two types of melts were used to produce slags studied in this investigation. The first series of smelts made to determine proper flux addition were produced in a 4 lb Ajax induction furnace. The charge, consisting of ore with the proper flux addition, was heated in a graphite crucible until fluid, held fluid for a sufficient time period to obtain 1-5 pct FeO content, and poured. Because of the small size of the charge only the final sample of these melts could be examined. In the melts made in the 50 lb arc furnace, however, grab samples taken at 10 min. intervals between time of initial melting and final pouring were available for examination. These samples allowed a much clearer picture of the course of reaction and crystallization. amounts of ferrous oxide and reduced titanium compounds is opaque to transmitted light. Therefore, all petro-graphic studies had to be made on polished slag sections. A representative sample of slag was cut or broken, mounted in a thermosetting plastic, ground flat using 400 grit silicon carbide, the coarse scratches removed with 600 grit silicon carbide and polished on billiard cloth using levigated alumina. Rouge was avoided because of the entrainment of the red particles in pores in the slag, causing a possible confusion with some of the mineral phases. In order to prevent sample projection above the plastic surface red bakelite was used to hold the sample, and backed up with clear lucite. In this manner sample labels could be permanently retained in the mounting. The polished samples were examined on a Bausch and Lomb metallograph at magnifications of 250 X, 500 X, 1000 X and 1800 X. The instrument was equipped for examination of specimens under bright field illumination and with crossed nicols. A magenta tint plate to aid in color tone differentiation was also used. Petrology of Slags In order to determine the composition and mineral relatinos of a previously unreported system petrologically, it is essential that the starting composition, reaction temperature and final composition be known. The chemical composition of the ilmenite ore used in these smelts is given in Table 1, and the complete analysis of a typical high titanium, low iron slag is given in Table 2. In the winning of TiO2 from ilmenite by a smelting process it is necessary to produce a slag which will melt at an economically feasible temperature, remain molten as the iron is removed by reduction, be fluid enough to be readily removed from the furnace, contain a high percentage of TiO2 and a low percentage of reduced titanium com-

Jan 1, 1950

By A. J. Shaler

The subject of the mechanism of sintering has received much attention in the past few years, particularly since the beginning of the series of AIME seminars in powder metallurgy of which this paper introduces the fourth. In the first of these, F. N. Rhines1 brought together and discussed the available experimental data on the sintering of pure metallic powder, and succeeded in bringing to a sharp focus the attention of workers in this field on the established observations which a satisfactory theory must explain. Several other authors3,5,6 have, in the last few years, studied the phenomena that occur when cold metallic powders, loose or in the form of compacts, are first brought to elevated temperatures. Some workers&apos; in the field of friction have recently studied the adhesion of solid metal surfaces when they are brought into close contact. These researches have indicated that several separate mechanisms operate simultaneously, at least during the first part of the sintering process. Some of them have been called transient mechanisms4 because they are in general not absolutely necessary to sintering. Powders may be so prepared and so treated that these transient phenomena do not take place during subsequent sintering. This does not mean, of course, that their industrial and scientific importance is any less than that of the steady-state phenomena. The latter are changes that go on during sintering no matter how the powders are made or treated; they cannot be divorced from sintering. One way to analyze the process of sintering into its component parts is perhaps to distinguish between these transient and steady-state phenomena. Some of the transient phenomena have been studied in the past few years. Huttig3 has shown that, when the temperature of metallic powder is slowly raised, the following events generally occur in order: (1) physically adsorbed gases are desorbed; (2) there is an atomic rearrangement of the surface, a sort of two-dimensional "surface-reciystallization"; (3) there is a breakdown of chemically adsorbed surface compounds; (4) there is a recrystalliza-tion in the volume of the metal. All these changes are shown by Huttig and his coworkers to be completed fairly rapidly at lower temperatures than those generally used in sintering and are therefore not a part of the mechanism whereby the density of a mass of powder continues to change after long heating at an elevated temperature. But the first and third of these changes release gases in quantities which may or may not help to control the steady-state mechanisms, depending on when the voids become isolated from the outside of the compact. Among the phenomena studied by Steinberg and Wulff,8 there is the effect on sintering of residual stresses arising from the pressing operation. They found that the lateral surfaces of a green compact of iron are under a longitudinal residual tension-stress of the order of magnitude of half the yield-point for solid iron. If the outside surface is in tension, the core must be under longitudinal compression. When the compact is heated, the surface residual stress is thermally relieved first, and the compact therefore initially expands in the direction of its axis. This is a transient phenomenon, if for no other reason than the possibility of sintering unpressed powders, as demonstrated by Delisle,9 Libsch, Volterra and Wulff10 and others.1 The subject of recrystallization is dealt with further in a separate section, in view of its prominent place in sintering literature. It, too. is one of these transient phenomena. Among the steady-state parts there may be distinguished the attraction between particles and its consequences, the spheroidization of voids in the compacts, and the densification or swelling of the compact. There is considerable evidence4,7 showing that cold metallic surfaces, when brought to within a few interatomic distances of one another, are attracted to each other by forces of the order of many thousands of pounds per square inch. A calculation, discussed in greater detail in another section, shows that this force changes but slightly when the temperature of the surfaces approaches the melting point. Actual measurements of forces of adhesion of this magnitude have been made by Bradley12 on some nonmetals, but none has yet been made on cold or hot metals. This force is of sufficient magnitude to cause some plastic deformation in powder compacts, as will be shown below. A second force of steady-state nature is due to the surface tension, which probably has the same origin as the force of attraction between surfaces.164 A paper by Udin, Shaler, and Wulff1,3 gives the results of precise direct measurements of its value for solid copper. The demonstration of the tendency for the surface tension to shrink a pore was long ago given by Gibbs.17 He showed that its effect on a curved surface between two phases is equivalent to a pressure perpendicular to that

Jan 1, 1950

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By J. E. Worthington, W. H. Spence, I. T. Kiff

Gold was discovered at the Haile mine in Lancaster County, South Carolina, in 1827 or 1828, and since that time the mine has been worked intermittently by both open-pit and underground methods until its forced closure in 1942 by World War II. Production figures are incomplete, especially for the early years, but the total gold produced is estimated to have been greater than 200,000 oz. Thus, the Haile mine has been the most productive gold mine in the eastern United States. The upper, residually enriched ores were relatively rich, but the bulk of the production has come from the mining of lower grade ores. General Geology The Haile mine is located in late Precambrian or early Paleozoic rocks of the Carolina slate belt at the edge of the Atlantic Coastal Plain [(Fig. 1)]. The metamorphic grade is lower greenschist facies and the rocks have been folded into a sequence of northeast-trending isoclinal folds. The gold is associated with siliceous, pyritic, and kaolinized felsic pyroclastic and tuffaceous rocks in an interbedded volcanic and volcanoclastic sequence of felsic to mafic tuffaceous rocks and argillaceous sediments [(Fig. 2)]. The ore bodies occur in two northeast trending zones approximately 500 m apart; each zone is 30-70 m wide and 600 m or more in length, with possible extensions to the east beneath the Coastal Plain sediments. Mineralogy. Gold in the Haile mine is always associated with siliceous and/or pyritic ores. The gold occurs in at least three states: As native gold as originally deposited; as residual gold derived from the breakdown of pyrite; and as gold included in pyrite. Major associated minerals in addition to quartz and pyrite are kaolinite, sericite, and iron oxides. Minor molybdenite, arsenopyrite, pyrrhotite, copper sulfides, sphalerite, rutile, and topaz are also present. Petrology. The gold-bearing ore zones vary from highly siliceous rocks to pyritic massive sulfide lenses. This variation is most easily seen today along strike from the Haile pit to the Red Hill pit. Ore grade material still exposed in the wall of the Haile pit consists of a highly siliceous and very thinly bedded rock containing minor pyrite. Along strike, the character of the mineralization changes to pyritic massive sulfide lenses occurring interbedded with siliceous horizons at the Red Hill pit. The siliceous rocks vary from the thinly-bedded material as just described from the Haile pit to silicified fragmental-appearing rocks to totally recrystallized cherty rocks lacking any recognizable primary features. Scattered, apparently at random, throughout the very thinly-bedded and very fine-grained ore face of the Haile pit are seemingly anomalous silica-rich clasts or concretions up to 5 cm in diameter which will be discussed later in this paper. Alteration. One of the most striking features of the Haile deposit is the alteration mineral assemblage which is intimately associated with the siliceous and pyritic ores. This altered material has been intersected in drill core at depths greatly exceeding the modern weathering profile and is, therefore, of hydrothermal origin rather than from supergene processes. This "sericite," actually a fine-grained mixture of sericite, kaolinite, and quartz, can be shown to stratigraphically underlie the gold- quartz-pyrite zone, and is well exposed in the open pit just southeast of the Haile and Bumalo pits. Relict textures indicate that this highly altered material was originally a felsic ash flow. Other similar alteration zones have been found in outcrop and drill core underlying the remaining ore bodies. Thus each of the mineralized zones consists of two parts: A siliceous and/or pyritic gold-bearing ore zone which is stratigraphically underlain by a zone of high alumina minerals, in this case sericite and kaolinite along with variable amounts of quartz. A green chrome mica, presumably fuchsite, is present in trace amounts in the high alumina zone. Genesis An adequate model to explain the origin and distribution of the gold deposits in the Carolina slate belt is presently lacking. Worthington and Kiff1 suggested a volcanogenic origin for certain gold deposits in the North Carolina slate belt from the waning exhalations of felsic volcanic piles. They also pointed out that such an origin has similarities to many epithermal precious metal deposits located in more recent volcanic piles in the western United States. A further key to the understanding of the genesis of the gold mineralization at the Haile mine is the close association of the mineralization in siliceous and sulfidic horizons to the genetically related and stratigraphically underlying high alumina alteration. Such high-alumina alteration is common around felsic volcanic centers in the Carolina slate belt and the mineralogy as seen today consists of some combination of kaolinite, sericite, pyrophyllite, kyanite, andalusite or sillimanite depending on the local prevailing grade of metamorphism. Accompanying the high-alumina alteration are large quantities of pyrite and iron-oxide minerals as well as characteristic minor accessory minerals often including base metal sulfides, fluorine-bearing minerals (topaz, fluorite, apatite), titanium-bearing minerals (ilmenite, rutile),

Jan 1, 1981

By P. N. Richards, M. K. Ormay

Commercially hot-rolled low-carbon steel strip may have one of two basic types of orientation texture, depending upon the amount of a iron which was present during the finishing passes. The changes in these textures with varying amounts of cold reduction up to 95 pct have been determined for the sheet surface plane and for parallel planes down to the mid-plane. The development of cold reduction textures has been reassessed on the basis of (200), (222). and (110) stereographic pole figures and pole density or inverse pole figure values. In agreement with the literature, it is shown that the textures can be described in terms of partial fiber textures but alternative descriptions are given for one of the fiber textures, in order to more closely correlate with experimental data. One partial fiber texture consists of orientations of the type (hkk)[011] extending from (100)[011] to {322}(011) in agreement with the literature. At moderate amounts of cold reduction, a second partial fiber texture forms with a <331> fiber axis inclined 20 deg to the sheet normal and a range of orientations centered on one close to (1 11)[112] and reaching to (232)[101] or (322)[011]. An alternative description involves a (111) fiber axis parallel to the sheet normal but capable of rotation about the rolling direction with rotation about the fiber axis. ORIENTATIONS developed in low-carbon steel strip after cold reduction are of commercial importance because they control, in part, the final preferred orientations after subsequent annealing. The method of control however is not understood completely. Some preliminary work indicated that the cold-reduced orientations and the subsequent annealing textures of commercial low-carbon steel were dependent on the orientations present in the material before cold reduction, that is, those present in the hot-rolled strip but, to date, the effects of initial orientations have not been extensively investigated. For this reason, much of the information given in the literature on development of preferred orientation is difficult to assess as details of initial texture and processing conditions are often inadequate or are altered by a subsequent heat treatment such as normalizing.&apos; It is known2 that anomalous results for near surface orientations may be obtained if lubrication during cold rolling is not adequate but whether lubricant was used during the experiments has not always been given, nor has the exact depth below the surface at which determinations have been made. A comprehensive review of cold rolling textures has been made recently by Dillamore and Roberts&apos; and more restricted recent reviews are due to stickels4 and Abe.5 Based largely on the experimental work of Bennewitz,1 reviewers have accepted that the preferred orientations produced on cold reducing low-carbon steel can be described in terms of two partial fiber textures as follows: Partial Fiber Texture A which has a (011) direction in the rolling direction and includes orientations within the spread from (211)[011] through (100)[Oll] to (211)[011.]; there is some controversy as to whether it extends as far as the orientation (111)[011]. As Dillamore6 has observed, the extent of this partial fiber texture depends on the intensity levels selected. Partial Fiber -texture B which has a (011) direction located 60 den from the rolling direction in the plane containing the rolling direction and the sheet normal. There are two directions which satisfy these conditions and orientations in this partial fiber texture extend from (21l)[0ll] through (554)[225] to (121)[101]. The orientations {211}(011) are members of both partial fiber textures A and B and it can be noted that a variant of {554)<225> is within 6 deg of a variant of {111}(112). Barrett7 had postulated earlier that, in addition to orientations which would fall into partial fiber texture A, a true fiber texture with a (111) direction in the sheet normal was present after heavy cold reduction. This fiber texture would include orientations such as {111}(011) and {111}(112). Later investigators, notably Bennewitz,&apos; have discounted this, mostly on the ground that the partial fiber textures A and B, as described above, contain all the strong orientations that have been observed. However in other work it has been reported2 that (222) pole density or inverse pole figure values show a continuing increase with increasing reduction by cold rolling and give values considerably greater than for any other low indices plane. Thus it could be inferred that a (111) fiber texture as described by Barrett would be one which becomes more dominant with increasing cold reduction, whereas Bennewitz&apos; concluded that components such as {554)(225) in partial fiber texture B began to decrease in intensity at high reductions. Following Bennewitz, one would expect a decreasing (222) pole density value (parallel to the sheet normal) with increasing cold reduction. Because fiber textures consist of grains with a range of orientations that have one axis in common, it has been inferred that during deformation the crystal orientations rotate about the fiber axis&apos;74 and that the orientations of crystals that at one stage belong to one fiber texture can rotate on further cold reduction into the other fiber texture through an orientation in which the two fiber textures intersect.&apos; For example,

Jan 1, 1970

By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.&apos; reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By N. L. Svensson

The model developed by Tuylor for the calculation of Polycrystalline yield strength has been applied to the case of an aggregate hawing a preferred orientation. In general this procedure requires the specification of texture by means of weighting factors applied to specific orientations. The problem to which the model has been applied is that of the yield-strength aniso-tropy of cold-rolled aluminum whose rolling texture was described as a combination of (110)[112] and (311) [112] In this case yield-strength anisotropy is defined by the rutio of yield strength measured at an angle 8 to the rolling direction to that measured along the rolling direction. The method of calculation of yield-strength ratio as a function of ? is described and the results show good agreement with experimental values. The orthotropic yield criterion suggested by Hill has been applied to the results and the strain ratio R also calculated as a function of ?. This has been compared with calculations using the method suggested by Elias, Heyer, and Smith which does not exhibit suck good agreement with observation. one deficietlcy of the method presented is that the strain ratios used by are those applying to iso-Irobic materials. The method should therefore be reg-clrded only as a first abbroximation to the prediction of anisotropy. THE problem of calculating the stress-strain characteristics of polycrystalline aggregates from the properties of single crystals has attracted attention for a number of years. The most important contributions to this study have been those due to: Sachs,&apos; Cox and sopwith,2 Taylor,3 Kochendorfer,4 Batdorf and Budiansky,5 Calnan and Clews,6 Bishop and Hill,7,8 Kocks,9 Budiansky, Hashin, and sanders, 10 Kroner,11 Cyzak, Bow, and payne, 12 Budiansky and Wu,13 and Lin.14 While the earlier work has been largely superseded, recent developments tend to support Taylor&apos;s solution" within the restriction imposed by his assumptions. The essential features of Taylor&apos;s approach were: 1) the material is rigid-plastic; 2) each grain experiences the same strain components as the aggregate as a whole (the problem was that of uniaxial deformation with principal strain components in the ratio 3) all regions of each grain deform uniformly; 4) work hardening occurs equally on all slip systems. While Bishop and Hill7 have generally validated this approach, there has been some criticism offered. Kocks? as pointed out that since multiple slip must occur the single-crystal data must be determined from orientations arranged such that polyslip takes place. Boas and Hargreaves,15 and others, have shown experimentally that the strain distribution within grains is not uniform, the strains in the vicinity of grain boundaries being less than those in the center of the grains. Both of these criticisms can be largely offset by the suitable choice of single-crystal critical shear stress. However, for the problem analyzed below, the critical shear stress is not directly used and, consequently, these criticisms lose their importance. The more recent contributions have attempted to obtain a more complete analysis by considering an elas-toplastic material and considering interactions between grains of differing orientations. Lin14 has considered the early stages of yielding for a polycrystalline aggregate having specific regions of defined slip plane orientations. On the other hand, Budiansky and Wu13 have allowed for these interactions for randomly disposed grain orientations and have calculated the polycrystalline stress-strain curves for crystals exhibiting either elastic-ideally plastic or kinematic hardening characteristics. This work has shown that yielding commences when the macroscopic stress is 2.2 times the critical shear stress for slip in a single crystal (7,). The yield stress-strain curve then rises becoming asymptotic to a value of 3.072 7,. This is close to the value obtained by Bishop and Hill (3.06) in their confirmation of Taylor&apos;s method. This, of course, is to be expected since, at large strain values, the elastic strains are negligible and the rigid-plastic model is satisfactory. The results of Budiansky and Wu indicate that the result obtained by Taylor is 7.7 pct high at a plastic strain which is two times the elastic strain at the initiation of yield. By defining the anisotropy in terms of relative values, the ratio of yield strength at orientation ?, to that measured in the rolling direction, the effect of the discrepancy in Taylor&apos;s solution is considered to be of lesser consequence. Therefore, it is anticipated that an analysis based on Taylor&apos;s solution, which can be quite straightforward, should provide a reasonable estimation of the anisotropy of materials having a preferred orientation texture. OUTLINE OF TAYLOR&apos;S METHOD In fee metals there are four possible slip planes (the octahedral planes) and in each there are three possible slip directions (the edges of the octahedron), that is a total of twelve possible slip systems. von Mises16 has shown that at least five independent slip systems must become operative in each grain of the polycrystalline aggregate in order to preserve continuity of strain. With this geometrical requirement as basis and the assumptions previously listed, Taylor determined the operative slip systems for a number of orientations of the tensile stress axis specified in the unit stereographic triangle. For the ith slip system, the critical shear stress

Jan 1, 1967

By G. R. Love, M. L. Picklesimer

Aboue 950°C the Nb-Zr system consists of a completely miscible bcc solid solution, commonly called the phase. Between 950 and 600°C, and between 20 and 85 pct Nb, the phase deconlposes, after sunciently long times, into two bcc solid solutions. The pct Zr alloys are conveniently descibecl with T-T-T (time-temperature-transformation) curves having a nose at about 2 hr at 700°C. The reaction rate varies only slowly with zirconium content and negligibly with oxygen contanzination; it is speeded up by a factor of 10 to 15 by 90 pct cold ulork and slowed dou by n factor oj 10 to 30 by a two-hundrecljold increase in grain size. Nb-r alloys with compositions between 40 and 85 pct Nb have been the basis for the majority of commercially important superconducting materials. In part because of their commercial promise, more is known about these alloys than about most other high-field superconducting materials. At the same time, there is considerable disputed or incomplete metallurgical information. For example, although Rogers and tkins&apos; indicate a monotectoid reaction at approximately 600°C and a two-phase 01 + 0, field extending between 20 and 85 pct Nb and to a maximum of 95OGC, erhout&apos; has reported that this entire region would be a single homogeneous B were it not for oxygen contamination. Again, although it has been shown that relatively short-time heat treatments in the vicinity of 700CZ significantly improve the ability of short wire samples to carry high currents in high magnetic fields at 4.2K, these observations have never been fully correlated with the structural change or changes occurring during the anneal. We intend to investigate in detail the effect of metallurgical variables, including heat treatment, on the superconducting properties of hard superconductors. To verify that our experimental techniques are valid and to establish a relative standard against which other materials may be measured, we feel it advisable to know the behavior of the Nb-Zr alloys under a variety of processing conditions. As an initial step toward this goal, we have determined in detail the kinetics of the transformations in Nb-Zr alloys. EXPERIMENT A number of problems had to be solved before beginning any fruitful work on the reaction kinetics in this system. While solving some of these problems, either by chance or by design, small amounts of information were obtained about alloys containing 40, 50, 60, 65, 67, 70, and 75 pct Nb, bal. Zr. In addition, a large range of grain sizes and a range of temperatures considerably greater than the range indicated by Rogers and Atkins phase diagram were examined. We will, however, report in detail only the results obtained for the Nb + 33 pct Zr and Nb + 25 pct Zr alloys at three grain sizes, two levels of oxygen contamination, and the temperature range 550 to 950°C. These data are most complete, but the other data are sufficiently complete to indicate the kind and magnitude of the variation of the transformation kinetics outside this range. The first and most difficult problem encountered in this inquiry was one of sample homogeneity. When Nb-Zr alloys are arc- or electron-beam-melted on a cooled copper hearth, solidification is sufficiently slow that there is appreciable coring in the cast structure and a large variation of grain size across the button thickness. Both these factors significantly affect the apparent reaction rate in the system. A two-step solution to the problem was attempted; an arc-melting and drop-casting technique has been developed by conald that greatly reduces the as-cast grain size and virtually eliminates coring segregation. Ingots made in this way exhibited no detectable (3 pct maximum) zirconium segregation. Before it was evident just how good this technique was, we attempted to supplement it with rather long-time, high-temperature annealing of the cast ingots. This annealing was carried out in evacuated and sealed (seal-off pressures < 1.0 x 106 torr) quartz capsules lined with tantalum foil at 1400 to 1450 C for 8 to 72 hr. There were two principal effects of this treatment: the grain size increased to a fairly uniform 150 p, and the surface and all grain boundaries near the surface acquired a film of a second phase, tentatively identified as an oxide (possibly additionally contaminated with silicon). There was no evidence that this 1400 C treatment had affected the zirconium segregation. High-temperature annealing was subsequently used only for grain-size control, but anneals of longer than 4 hr at temperatures greater than 1000°C were performed in dynamic vacuums (pressure no greater than 1.0 x lo torr). Any contamination resulting from these treatments was well below the limits of detection of our techniques. All samples, as cast, were cold-swaged to at least 85 pct reduction in area. The samples called cold-worked were tested as swaged. The minimum re-crystallization anneal for these alloys was about 12 hr at 1050 C; this produced an equiaxed grain diameter of about 4 to 8 P. Annealing for 4 hr at 1450°C produced a grain size of about 80 to 150 p; and annealing for 4 hr at 1650aC, close to the melting point of many of these alloys, produced a grain size of 0.5 to 1.0 mm. At all temperatures, the larger grain size was

Jan 1, 1967

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith&apos; while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith&apos;s experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours&apos; exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By H. W. Reinhardt, J. W. Dally

A dynamic photoelastic analysis of stress waves interacting with a free surface is described. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb N,). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. The mechanics of rock breakage by means of explosives has received considerable treatment by many investigators including Duvall, Obert, Broberg, Rinehart, and Langefors1-11 over the past two decades. Indeed in more recent years several texts12-15 have been written on the topic, treating a wide variety of subjects which are logically related to the modern technique of rock blasting. In rock blasting the chemical energy of a concentrated explosive contained in a relatively small diameter borehole is utilized to fragment the rock. The explosive is transformed into a gas with enormous pressures which exceed 10-5 bars18 This high pressure shatters the rock in the area adjacent to the borehole and produces dilatational and distortional stress waves which propagate radially away from the borehole. The state of stress associated with these outgoing waves produces a system of cracks which extend for a few feet from the borehole. The breakage produced in this manner is limited as the dynamic stress in the pulse attenuates markedly with distance. In the absence of a free surface, the stress wave propagates away from the source without further fracture. With a free face of rock near the drill hole, another mode of breakage occurs which is due to scabbing failure of the layer of rock adjacent to the free face. These scabbing failures are produced by the reflection of the incident waves and the conversion of compressive stresses into tensile stresses sufficiently large to fracture the rock. The detailed nature of the interaction of the stress waves with the free surface is complex and difficult to treat analytically. However, dynamic photoelasticity offers an experimental approach which gives a fullfield visual display of propagating stress waves and the reflection process. Applications of static photoelasticity to solution of problems related to mining technology have become relatively common (see, for instance, Refs. 17 and 18) with a plastic model loaded to produce a state of stress representative of that occurring in the workings of a mine. The application of dynamic photoelasticity is ex tremely limited. Tandanand and Hartman19 have used a multiple spark camera to study fracture in glass and plastic plates impacted by a chisel-shaped tool. This paper describes a dynamic photoelastic analysis of stress waves interacting with a free surface. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb-N6). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. Experimental Procedure The model illustrated in [Fig. 1] was fabricated from a sheet of Columbia Resin CR-39 to represent a bench with a fixed bottom. Properties of the CR-39 pertaining to these dynamic experiments are listed in [Table 1]. Scribe lines on 1-in. centers are used to identify locations along the bench face. The bench height was 8 in., the burden was 3 in., and the overall dimensions of the sheet, 16 and 18 in., were large enough to eliminate reflections from nonessential boundaries during the period of observation of the dynamic event. To simulate a charge in a borehole, a groove 0.062 in. wide and 0.080 in. deep groove was cut into the sheet from one side. The lower end of the groove was 1 in. or 1/3 the burden distance below the bottom of the bench. The upper end of the groove was 3 in. or one times the burden distance below the upper level of the bench. The groove was packed with 60 mg of Pb No per in. of length, and ignited with a bridge wire detonator. Four different ignition procedures were used to examine the effects of detonation direction on the stress wave interaction with the free face of the bench. In Test 1 the line charge was ignited at the top and the line charge detonated downward. In Test 2 the line charge was ignited at the bottom and the charge burned upward. In Test 3 the charge was ignited in the center with the top half burning upward and the bottom half burning downward. Finally in Test 4 the line charge was ignited at both ends simultaneously. Sixteen high-speed photographs of the photoelastic fringe patterns representing the stress wave propagation were recorded for each of the tests. A Cranz-Schardin multiple spark gap camera 20,21 was operated at framing rates which were systematically varied from 110,000 to 250,000 frames per sec during each test.

Jan 1, 1972

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the &apos;a; and &apos;c,,&apos; edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.&apos; LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By T. R. A. Davey

IN 1947 the author became interested in the fundamental aspects of the desilverizing of lead by zinc, conducted some experimental work, and searched the technical literature for all available fundamental data. Since then a revival of interest in the subject in Europe resulted in the appearance of quite a number of papers. It became evident that it would be more profitable to collect together and examine thoroughly the results of various workers, than to attempt to duplicate the experimental determinations. There are many inconsistencies in the various publications, and it is opportune to review at this time the present status of knowledge on the Ag-Pb-Zn system. There is also a need for a clear description, in fundamental terms, of the various desilverizing procedures. This paper is presented in four sections: 1—There is an historical review of the origins of the Parkes process, of the results of many attempts to find a satisfactory fundamental explanation for the phenomena, and of the modifications proposed to date. 2—A diagram of the Ag-Pb-Zn system is presented. This is believed to be free of obvious inconsistencies or theoretical impossibilities, although thermodynamic analysis subsequently may reveal errors. 3—The fundamental bases of the various desilverizing procedures, which have been used up to the present day, are described; and a new method is suggested for desilverizing a continuous flow of softened bullion in which the bullion is stirred at a low temperature in two stages producing desilverized lead at least as low in silver as that from the Williams continuous process and a crust which, on liquation, yields a very high-silver Ag-Zn alloy. 4—A suggestion is made for the revival of de-golding practice, following a recently published account which does not seem to have attracted the attention it deserves. The terms "eutectic trough" and "peritectic fold" as used in this paper are synonymous with "line of binary eutectic crystallization" and "line of binary peritectic crystallization" as used by Masing.&apos; The German literature on ternary and higher systems is rather extensive and a fairly general system of nomenclature has arisen, whereas in English usage the corresponding terms are not as well established. For this reason the meanings of terms used in this paper, together with the equivalent German terms, are given as follows: 1—Eutectic trough—eutektische rinne: line at which a liquid precipitates two solids S1 and S2 simultaneously. If the composition of a liquid which is cooling reaches this line, it then follows the course of this line until a eutectic point is reached, or until all the liquid is exhausted. The tangent to the eutec-tic trough cuts the line joining S1S2. 2—Peritectic fold—peritektische rinne: line at which a solid S1 and a liquid L transform into another solid S2. If the composition of a liquid which is precipitating S1 reaches the line, on further cooling only S2 is precipitated. The liquid composition moves from one phase region (L + S1) into the other (L + S2), and does not follow the course of the boundary. The tangent to the peritectic fold cuts the line S1S2 produced nearer S,. 3—Liquid miscibility gap, or conjugate solution region—mischungslucke: the region within which two liquid phases coexist in equilibrium over a certain range of temperature. A system whose composition is represented by a point in this region comprises one liquid at high temperature; then as the temperature is progressively reduced, two liquids, one liquid and one solid, one liquid and two solids, and finally three solids. 4—Liquid miscibility gap boundary—begrenzung der flussigen mischungsliicke: the line along which the surface of the miscibility gap dome, considered as a solid model, intersects the surrounding liquidus surfaces. 5—Tie lines—konoden: lines joining points representing the compositions of two liquids, a liquid and a solid, or two solids, in equilibrium. In binary systems the only tie lines customarily drawn are those through invariant points, e.g., through the eutectics of the Pb-Zn and Ag-Pb systems, or the various peritectics of the Ag-Zn system, as in Figs. 1 to 3. In ternary systems it is desirable to draw sufficient tie lines to indicate the slopes of all possible tie lines. 6—Ternary eutectic point—ternares eutektikum: point at which liquid transforms isothermally to three solids, S1, S2, and S Such a point can lie only within the triangle 7—Invariant peritectic (transformation) point— nonvariante peritektische umsetzungspunkt: (a) — On the miscibility gap boundary, the point at which two liquids and two solids react isothermally so that L, + S, + L, + S2. (b)—On the eutectic trough, the point at which a liquid and three solids react iso-thermally so that L + S, + S2 + S3. Such a point must lie on that side of the line joining S,S which is further from S,. (c)—A further possibility, not found in this ternary system, is that the point is at the intersection of two peritectic folds when the reaction concerned is L + S, + S, + S Historical Introduction Karsten discovered in 1842 that silver and gold may be separated from lead by the addition of zinc.2 Ten years later Parkes used this fact to develop the well known desilverizing process which bears his

Jan 1, 1955

By James W. Dally, William L. Fourney, Anders Ladegaard Peterson

For the past 3 years, the authors have been conducting research sponsored by the National Science Foundation (RANN) to improve the process of excavation by drilling and blasting. The approach followed has been experimental where the development of stress waves and fractures initiated at the bore hole have been investigated in order to obtain a complete understanding of the dynamic fracture process. The second step in the approach has been to introduce modifications in the drill and blast procedure which will permit closer control of the fracture process. The laboratory investigations involve high speed photography where the dynamic fracture process is recorded with a Cranz-Schardin 1, 2 multiple-spark camera. The camera is equipped with 16 spark gaps which are pulsed at 25 K volts to produce an intense but very short (0.5 sec) flash of light. The camera is capable of recording 16 photographs of a dynamic event at framing rates which can be varied from 30,000 to 1,500,000 frames per second. The exposure time is sufficiently short to stop motion associated with detonating explosive charges and to make visible the details of the fracture process at a bore hose. The bore hole in a massive intact rock formation is modelled with a two dimensional plate containing a circular hole to represent the bore hole. The model material employed is a transparent polyester known commercially as Homalite 100.* This polymeric material is extremely brittle as evidenced by its extremely low fracture toughness of [ ]. The fracture toughness is a measure of the ability of a material to resist the propagation of flaws or small cracks. In comparison, Schmidt3 has recently measured the fracture toughness of Salem limestone and determined [ ]. Thus, the Homalite 100 should closely model the brittle nature of rock where fractures occur at small flaws and propagate without any apparent plastic deformation. Homalite 100 is also birefringent, which indicates that it becomes optically anisotropic when subjected to either static or dynamic loads. Circularly polarized light is transmitted through the loaded Homalite 100 model in a polariscope4 and the birefringence produces an optical interference pattern which is called a fringe pattern. For dynamic photoelasticity, the multiple-spark camera is equipped with polaroid filters to produce the circularly polarized light required to generate the photoelastic fringe patterns. An example of a singlespark frame showing a fringe pattern from a typical experiment is presented in [Fig. 1]. The photograph was taken 0.000072 sec (72 sec) after the detonation of the explosive charge. The circular fringes are due to the outgoing dilatational or P type stress wave and travel with a velocity of 85,000 in. per sec (2260 m/sec) in the Homalite 100. The P wave is followed by a second lower velocity stress wave known as the shear or S type wave which propagates at a velocity of 49,000 in. per sec (1245 m/sec). In the local neighborhood of the bore hole, several radial cracks are visible. These cracks propagate at essentially a constant velocity of 15,000 in. per sec (380 m/sec) prior to arrest. The fringes about the crack tips and in the local region of the bore hole are primarily due to the residual gases contained in the bore hole after the explosive charge was detonated. Sixteen frames similar to this one are recorded during the experiment to give full field visualization of the dynamic event at 16 discrete times over its duration. The fringe order number N is related to the difference in the principal stresses of and 02 according to a stress optic law4: [ ] where f0 = material fringe value, and h = model thickness. The wholefield dynamic-fringe patterns provide a basis for simultaneously observing the interaction between propagating cracks and the stresses which drive these cracks. Fracture Control Experiments Improvements in the efficiency of the drill and blast procedures must involve close control of the fracture process following the detonation of an explosive charge in a bore hole. By control it is implied that the number of cracks initiated and the location of each crack on the wall of the bore hole can be specified. Control also, involves orienting each crack and maintaining the crack path and velocity until the specified crack length is achieved. If the entire fracture process can be controlled, then rounds can be designed to optimize volume removed. fragment size and minimize costs. One area of blasting where fracture control is vitally important is in underground excavation where the strength and stability of the rock walls must be maintained and smoothness and precision of the walls must be achieved. The smooth blasting method is one of the most commonly employed procedures for achieving some degree of fracture control. In smooth blasting, the central region of material is first removed, and then the final row of closely spaced undercharged or cushioned holes are fired to remove the final volume and produce a smooth wall. In some instances, unloaded or dummy holes between the loaded holes are recommended to guide the fracture plane. This investigation pertained to an evaluation of 3 features of the smooth blasting process. These included (a) the effect of stress reinforcement on fracture by simultaneously firing 2 charges; (b) the influence of a dummy hole on control of the fracture planes between 2 simultaneously fired charge holes; and (c) the influence of dummy hole spacing on fracture plane control.

Jan 1, 1979

By A. Y. Bethune, W. G. Woolf

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process&apos; for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt&apos;s earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.&apos;s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By W. G. Woolf, A. Y. Bethune

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process&apos; for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt&apos;s earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.&apos;s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By F. W. Schremp, V. L. Johnson

This paper discusses the results obtained from high temperature, high pressure filter loss studies in which field samples of clay-water, emulsion, and oil base fluids were used. High temperature, high pressure tests of some premium priced emrilsion and oil base drilling fluids show filter loss peculiarities that are not predicted by standard API tests. It is recommended that high temperature, high pressure filter loss tests be used to evaluate the performance of such fluids. Apparatus is described which proved to be satisfactory for evaluating filter loss behavior over a wide range of temperatures and pressures. INTRODUCTION The petroleum industry spends large sums of money each year on chemical treating agents for lowering filter loss and on premium-priced low filter loss drilling fluids. While it is an accepted fact that low filter loss is advantageous during drilling operations, it is questionable whether the present standard method of determining filter loss gives a reliable indication of the loss to he expected under bottom hole conditions. The purpose of this paper is to show that high temperature. high pressure filter loss tests Should be used to evaluate filter loss behavior of fluids for deep drilling. Concern over possible effects of filter loss on oil well drilling and well productivity dates back to the early 1920&apos;s. During the years 1922 to 1924, filtration studies were reported by Knapp,&apos; Anderson2 and Kirwan." These studies were the first to be reported in the literature on this subject. No further information was published on the subject until 1932 when Rubel&apos; presented a paper in which he discussed the effect of drilling fluids on oil well productivity. In 1935. .Jones and Babson constructed the first laboratory tester designed to study the effects of temperature and pressure on the filter loss behavior of clay-water drilling fluids. In a discussion of their investigations, Jones and Babsons stated, "Performance characteristics of a mud can he evaluated with considerable reliability by a single test at 2,000 psi and 200°F. Exact correlation between the results of performance test5 made under these conditions and the behavior of muds in actual drilling operations is of course impossible." Jones arid Babson apparently were well aware that at best laboratory tests can give only qualitative answers to the question of what is the actual behavior of a drilling fluid when subjected to deep drilling conditions. Jones&apos; presented a paper in 1937 in which he described a static filter loss tester to be used for routine filter loss tests. This instrument subsequently was adopted as the standard APl filter loss tester. In 1938, Larsen7 developed a relationship between filtrate volume and filtrate time that is in general acceptance today. Larsen was cognizant of the danger of estimating bottom hole behavior from filter loss measurements at room temperature. He tried to predict the effect of temperature on filter loss by relating temperature effects through the temperature dependence of filtrate viscosity. This was undoubtedly an over-sirriplification of the temperature dependence of drilling fluid filter loss. In 1940, Byck" published a summary of experimental results of filter loss tests made on six representative California clsy-water drilling fluids. He concluded that "no existing method will permit even an approximate determination of the filtration rate at high temperature from data at room temperature. It is necessary to measure filtration at the temperature actually anticipated in the well, or to make a sufficient number of tests at various lower temperatures so that a small extrapolation of these data to the anticipated well temperature may be applied." Byck&apos;s findings were presuma1)ly well accepted and recognized by drilling Fluid technologists, and yet, they did not lead to wide adoption of high temperature drilling fluid filtration equipment. This is evidenced by the fact that no addition information has appeared in print on the subject since 194). Study of Byck&apos;s data shows that there was a useful consistency in them. The fluids did not show predictable losses at high temperatures, but they did line up at high temperatures in approximately the same order that they lined up at low temperatures. That is, if a fluid appeared to be a good fluid with relatively low loss at low temperatures, it would also be a good fluid with relatively low loss at high temperatures. In the last decade. the above situation has changed. The drilling fluid art is markedly different from what it was. The outstanding change, as far as the present discussion is concerned, has been the adoption of wholly new types of drilling fluids. Oil base and emulsion drilling fluids have come in to wide use. It is, therefore, necessary- to re-examine previously satisfactory generalizations to see if they are still valid. It turns out. as might have been expected. that Byck&apos;s explicit generalization. already quoted, is still true. Filter losses at high temperatures cannot be predicted from filter losses at low temperatures. However, no further generalizations are valid now. Fluids of different chemical types show different general behaviors. No longer do the fluids line up approximately the same at high temperatures as they do at low temperatures. They may line up entirely differently. Special fluids exhibiting very low loss at low temperatures may have losses as high as those of ordinary clay-water fluids at high temperatures. This fact is highly significant, because premium prices are being paid for the special fluids.

Jan 1, 1952

By David Moskowitz, Ira Binder, Robert Steinitz

THE hard refractory borides of the transition elements of the 4th, 5th, and 6th groups of the Periodic System have been the subject of a number of recent investigations.&apos;-&apos; It is well known now that most of these elements form several different borides, and Kiessling8 has summarized the rules which govern to some extent the arrangements of the boron atoms in the various structures. Melting points of a few borides have been published." The systems Fe-B, Ni-B, and Co-B have been reported," but, as these borides are rather low melting, they are outside of the groups of boron compounds considered here. Brewer&apos; has tested the stability of various borides and estimated a number of eutectic temperatures between different borides, but in no case was the complete system of a transition metal and boron investigated. The phase diagram becomes of special importance if the preparation of the borides from the elements in powdered form is considered; the lowest eutectic temperature will determine the first appearance of a liquid phase. Also, the knowledge of high temperature phases, if they exist, is important for the preparation of bodies from these borides by hot pressing or sintering. During the investigation of various metal borides,7 it was found that there were more boride phases existing in the Mo-B system than reported by Kiessling." They occur, however, only at temperatures above 1500°C and were, therefore, not found by him. This led to a study of the equilibrium diagram of the Mo-B system. ranging from 0 to 25 pct B and from room temperature to the liquidus. Part of this investigation was reported during the "Research in Progress" session at the 1952 Annual Meeting of the AIME.11 Raw Materials and Preparation of the Borides The raw materials used were commercial molybdenum and boron powder, both supplied by the Molybdenum Corp. of America. The molybdenum powder was 99+ pct pure? while the boron powder contained about 83 to 85 pct B. A large percentage of the impurities in this powder was oxygen, with the rest formed by iron, calcium, and unknown substances. The low purity of the boron used was, however, not considered detrimental to the final product, as most of the impurities evaporated at the high temperatures at which the borides were formed. The final product always had a minimum purity of 96 to 98 pct (figured as molybdenum and boron), with carbon, iron, and probably oxygen being the remaining products. Carbon is usually present as graphite. The chemical analyses always confirmed the compositions which corresponded to the crystallographic structures as determined by X-ray diffraction, and the boron content of the finished product agreed closely with that of the starting mixture; no boron was lost during the boride preparation. The chemical analysis methods employed for molybdenum and boron were previously described by Blumenthal.12,13 The powders were mixed by hand in the desired proportions, compressed at room temperature under low pressure, and then heated under hydrogen to about 1500" to 1700°C in a graphite crucible to form the borides. Usually, the three well-known borides Mo,B, MOB, and Mo,B,, which are stable at room temperatures, were prepared in this way, and all other compositions were made by mixing these borides in various ratios or by the addition of molybdenum or boron powders for the very low or very high boron contents. Preparation of two-phase compositions directly from the elemental powders was tried only occasionally to check whether equilibrium could be reached in this way. Experimental Procedures The stable borides were mixed in the desired ratios and heated under hydrogen in graphite crucibles to various temperatures. The well insulated crucibles were heated in a high frequency induction furnace. Special care was taken to obtain exact temperature measurement, which proved much more difficult than originally anticipated. It is believed that individual temperature measurements have an error of less than ±25ºC, while melting or transformation temperatures are accurate within ±50°C. The temperatures were measured with an optical pyrometer which was aimed at the closed end of a graphite tube extending down into the crucible. close to the samples. Attempts to measure directly through the hydrogen exit stack failed. The crucible arrangement is shown in Fig. 1. Heating was done at a slow rate to be sure that the temperature inside the crucible was uniform. The specimens were kept at the final temperature for about 30 min. For the investigation of high temperature phases, some samples were quenched. They were heated, without atmosphere protection, in a very small graphite crucible which could be rapidly removed from the high frequency coil, and dropped into water. These quenched samples were afterwards annealed to establish the equilibrium at lower temperatures. The melting points or the positions of the solidus and liquidus lines were determined by heating the specimens to various temperatures and examining them at room temperature for evidence of a liquid phase. These results were checked later on by thermal arrest curves, especially to determine the exact position of the eutectic temperature line. For this purpose about 200 g of the boride were melted in a graphite crucible, in an arrangement similar to Fig. 1. Slow cooling was assured by very good

Jan 1, 1953