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By G. R. St. Pierre, S. W. Gilby

The equilibrium vapors established over Fe-Cr-Ni alloys containing up to 50 pct Cr at 1600°C were determined by collecting the effusate from thoria Knud-sen cells. From these data, the activities of iron and nickel in the ternary alloys have been calculated. In a separate set of measurements, a mass spectrometer was used to determine the activities of the three components in a series of Fe-Cr-Ni alloys. In binary Ni-Cr melts, the activity coefficient of chromium referred to pure solid chromium as standard state is less than one at low chromium contents but is greater than one for melts containing more than 30 at. pct Cr. For Ni-Cr melts containing less than 10 at. pct Cr, In ?Cr = 0.15-0.92 N2. Ternary activity diagrams for Fe-Cr-Ni alloys are presented. In iron-rich alloys, the interactions between the three components are negligible; however, in nickel-rich alloys, the three principal interactions have significant positive values. THE activities of components in binary Fe-Ni alloys have been measured both in the solid solution1-3 and liquid solution4-6 temperature ranges. The determination for Fe-Ni melts have been made by three different methods: transpiration,4 Knudsen-cell effusion with analysis of an accumulated condensate,' and Knudsen-cell effusion with direct measurements of relative component intensities by mass spectrometric methods.6 The results obtained by the three different methods in three different laboratories are in excellent agreement and considerable confidence is placed in the activity coefficients for Fe-Ni melts. At 1600°C, the activity coefficients in dilute solution are ?°Ni = 0.66 and ?oFe = 0.40 for the pure liquid components as standard states. Measurements made on solid solution Fe-Cr alloys7-10 indicate that the component activities are slightly greater than ideal. The measured activities in iron-rich Fe-Cr liquid alloy11-16 indicate almost ideal behavior for this system. The recommended activity coefficient of chromium in dilute solution in liquid iron at 1600o C, ?oCr, is 1.18 when referred to pure solid chromium as standard state and 1.04 when referred to pure undercooled liquid chromium as standard state." The conversion factor of 1.14 is based on a melting point of 1857°C and an enthalpy of melting of 4047 cal per g at. for chromium.21,37 The activity coefficient of iron in dilute solution in liquid chromium has not been measured. Activity measurements on solid Ni-Cr alloys have been made by several investigators.17-20 During the review of this manuscript, Fruehan12 published the results of a study on liquid Ni-Cr alloys at 1600°C. He used galvanic cells22 with ZrO2(CaO) as the electrolyte and Cr/Cr2O3 for the reference electrode. His results indicate that ?oCr in nickel at 1600°C is about 1.01 when referred to pure solid chromium and about 0.89 when referred to pure undercooled liquid chromium as standard state. The activity coefficient of nickel in liquid chromium is unknown. The compositions of vapors freely evaporating from some molten Fe-Cr-Ni alloys have been measured by Lyubimov, Granovskaya, and Berenstein.23 Their results, combined with known vapor pressures, indicate strong positive deviation for chromium in iron-rich alloys and strong negative deviation for chromium in nickel-rich alloys. EXPERIMENTAL PROCEDURES This research was undertaken to determine the activities of components in ternary Fe-Cr-Ni melts containing up to 50 at. pct Cr. At the initiation of the research, we decided to use a Knudsen-cell method wherein a portion of the effusing vapor is condensed on a cold plate.' The composition of the equilibrium vapor for each alloy composition is determined in this method by holding the system under constant conditions for a period of time sufficient to collect enough condensate on the cold plate for chemical analysis. The activities of components in ternary alloys can be calculated from such vapor composition determinations by Eq. [1].24

Jan 1, 1970

By Milan Matula

One of the main characteristics of the development of rock mechanics in some countries is a close cooperation between experts in rock mechanics and workers in related fields, including soil mechanics and engineering geology. The purpose of this chapter is to outline the contribution that engineering geology can make to rock mechanics and to present a few examples of engineering geology studies that have been used in solving some practical rock mechanics problems. Engineering geology investigations dealing with the influence of geological factors on the physical properties of rock materials and rock masses fall into three main categories : 1) Systematic study and correlation of the physical properties of the main rock types with the petrogenetic evolution that caused the differences in the properties of these various rock types. 2) Study of the heterogeneity and anisotropy of both rock materials and rock masses. 3) Delimitation of rock masses which are approximately uniform in physical properties (quasihomogeneous units). Delimiting of the quasihomogeneous rock masses is the main contribution that the engineering geologist can make to rock mechanics. This delimiting is based on the evaluation of many complex geologic factors, not on test results alone, and therefore is most effectively done by trained engineering geologists. The foregoing types of studies are being used in Czechoslovakia for several purposes, including : 1) the compilation of regional engineering petrologic data-that is, the systematic definition of the main rock types of the country in terms of their representative physical characteristics;

Jan 1, 1970

By Fathi Habashi

THE UNIT process of adsorption involves two steps: 1) Loading of the adsorbent. 2) Recovery of metal values from the adsorbent. Charcoal is the adsorbent commonly used in extractive metallurgy. The discovery of the adsorptive power of charcoal from solutions is generally accredited to Lowitz (1785), who observed that several dissolved organic substances were precipitated on charcoal. Graham was the first to demonstrate that inorganic substances were also adsorbed on charcoal. In 1830, he reported that iodine dissolved in KI solution was adsorbed on charcoal. Also calcium ions were adsorbed from limewater, as were lead ions from lead nitrate solution. The use of charcoal in metallurgy was first applied

Jan 1, 1970

As 1970 develops and industrial minerals stand at a crucial point in their progress, research and development programs appear to be the key needed to open up new uses for each mineral's future growth. Radically new processes are needed for making a host of new synthetic products from mineral raw materials which will more nearly meet the demanding specifications required for high performance in space, nuclear and defense applications. Consumer applications for high temperature environments will be needed and are important for continuing the nations economic mineral position. In addition, an acute materials problem limits the effectiveness of some of the newer concepts for controlling ail pollution. What is needed then, according to a report printed by the National Academy of Sciences, is the carefully planned development of a limited number of major centers at universities to provide for both basic research and training of personnel; the nurturing of interdisciplinary mechanisms for research and problem solving within these centers; the achieving of a better balance between physics and chemistry within research, emphasizing the chemical aspects of the material sciences; and the enhancement of a broader professional identity by unifying the various disciplines involved into a possible federation of existing societies which have an interest in the problems. [EE] presents its 1969 annual industrial minerals review, where individual authors evaluate the status of each industrial mineral and recount the major developments which occurred during the year.

Jan 1, 1970

By E. W. Dewing

ROLIN1 in 1961 published a phase diagram for the CaF2-Na3AIF6 system in which substantial (-20 wt pct) solid solubility of CaF2 in Na3A1F6 at the eutectic temperature (945°C) was indicated. The evidence was that the halt in cooling curves associated with the eutectic was lowered progressively on the Na3AlF6 side. H olm2 has recently confirmed the experimental fact, but attributes it to evaporation losses shifting the composition into the ternary NaF-CaF2-Na3A1F6 system with a consequent lowering of the eutectic temperature

Jan 1, 1970

By William E. Bruce

In recent investigation of drilling processes, the U.S. Bureau of Mines measured the operating characteristics of two percussive drills. Basically, this entailed measuring maximum piston velocities while drilling. The maximum piston velocity is not necessarily the same as the striking velocity. The latter is usually somewhat lower1 because most commonly used drills provide an air cushion which slows the piston just before it comes in contact with the drill rod. Penetration rates for the two drills were determined in nine rock types, and the physical properties of the same nine rocks were measured and tabulated. Then the penetration rates were plotted against the individual properties to determine the general relationships on which methods for predicting drilling rates could be based.2

Jan 1, 1970

By E. S. Shedd

Misch metal was electrowon from a treated bastnasite concentrate in a REF3-LiF-BaF2 electrolyte at 950° C. The metal was prepared and tapped from a 1,000-ampere cell, and nearly 100-percent utilization of the rare-earth oxide was achieved. Prolonged operation in a smaller cell (40 amperes) indicated that the composition of the misch metal product was reasonably constant, and no significant increase of impurities, with the exception of carbon, was noted.

Jan 1, 1970

By J. F. Boux

"The study of the total utilization of fly ash has involved all of the known technology in the processing of this waste material into useful products. In addition, a complete knowledge of all the possible uses of fly ash and its products in the market area was probably the most important factor in evaluating the theory and practical feasibility of the total utilization of fly ash from a single large supplyLaboratory tests carried out on the separation of fly ash into different fractions were shown to improve its value and utilization. Four main fractions were studied: a fine pozzolanic low-carbon fraction; a coarse fraction for light-weight aggregate production by pelletizing and sintering; a high-iron fraction; and a carbon-rich fraction. The term ""beneficiation"" here refers to a process of separating fly ash into more useful components.Laboratory and pilot sinter strand tests were employed to optimize the sintering capability and the quality of the heat-hardened pellets through a study of the agglomeration cycle in four principal heat zones, under controlled conditions of air flow, temperature and atmosphere, and including the controlled sizing of pellets.The suitability of the heat-hardened pellets as light-weight aggregate was evaluated in test batches of concrete, which were compared with concrete containing commercial lightweight aggregate of established quality.A study of beneficiated fly ash pozzolan as a partial cementitious binder component in normal and high-temperature cured concrete was reported in a paper at the re-cent Second International Fly Ash Symposium.Samples of raw and beneficiated Lakeview ash were compared with samples of other established high-quality fly ash pozzolans. The evaluation indicated the usefulness of beneficiated Lakeview ash as a pozzolan. Economic studies indicated that to accomplish the primary objective of total utilization of any single source of fly ash (in this case. fly ash from the Lakeview Generating Station, producing approximately 400,000 tons per year), a broad knowledge of the technology of various mineral processes was essential.The design of the fly ash processing plant had to be based on the disposal of all the raw fly ash produced by the generating station. This is contrary to the normal design of a processing plant in which raw materials are supplied and produced according to product demand. The design, therefore, had to be of such flexibility as to pro-duce as wide a variety of products as possible, and the ability to market them had to be well researched and understood."

Jan 1, 1970

By Wilbur I. Duvall, Wilson Blake

The microseismic method of detecting instability in underground mines was developed by the U.S. Bureau of Mines (USBM) in the early 1940's. ,3 The method relies on the fact that as rock is stressed, strain energy is stored in the rock. Accompanying the buildup of strain energy are small-scale displacement adjustments that release small amounts of seismic and acoustic energy. These small-scale disturbances, which can be detected with the aid of special geophysical equipment, are called micro-seisims or self-gene rated rock noises. It was further determined that as failure of rock is approached, the rate at which rock noises are generated increases. Thus, by monitoring a rock structure at intervals and plotting rock noise rates vs. time, a semi quantitative estimate of the behavior and stability of the structure can be made. Since sufficient use of the microseismic method is still being made by various mining and construction companies, USBM undertook a comprehensive review of the method and a study of the fundamental properties of rock noises. As all prior work on rock noises has been done with resonant-type geophones, which prevented any analysis of their vibration records, it was necessary to develop the instrumentation and field techniques in order that their properties could be investigated, such as their frequency spectrum and absorption characteristics, and to determine if both P and S-waves are generated by a rock noise. The aim of this program is the design of microseismic instrumentation which can be better utilized as an engineering tool than the presently available microseismic equipment. This new design, based on the basic properties of rock noises, should allow better utilization of these phenomena in the study and location of zones of incipient instability in both underground and open-pit mines. EXPERIMENTAL PROCEDURE To study the waveform of rock noises, it was necessary to develop a microseismic system with a broad bandwidth. To achieve high sensitivity and broad frequency response, commercial ceramic accelerometers were used. The present broad-band microseismic system consists of accelerometers as geophones, low-noise preamplifiers, high-gain amplifiers, and an FM magnetic tape recorder. This seven-channel system has a flat frequency response from 20 to 10,000 Hz, a noise level of less than 2.0 kv, and a dynamic range (including manual set attenuation) of greater than 100 db; it can detect signals with acceleration levels as low as 2 ug. The entire system is solid state and hence battery operated and portable (Fig. 1) Analysis procedures consist of playing back the 30-in-per-sec (ips) magnetic tape recordings at 1 7/8 ips to expand the time scale of a recorded rock noise event and then recording this on a high-speed direct-writing oscillograph. The oscilIographic records are then digitized and run through Fourier integral analysis computer programs to determine the frequency spectrum of a rock noise event. The oscillographic records are also examined visually to determine if both P and S-waves can be recognized in a rock noise waveform. Broad-band microseismic recordings have been made at field sites in a wide variety of rock types and in both underground and open-pit mines. Sites include the Kimbley Pit, Ruth, Nev.; the Galena Mine, Wallace, Idaho; the Colony Development Mine. Grand Valley, Colo.; the Cliff Shaft Mine, Ishpeming, Mich; and the White Pine Mine, White Pine, Mich. DATA AND DISCUSSION Analyses of the recorded data have shown that rock noise frequencies are very broad. Fig. 2 and 3 show typical rock noise events and their frequency spectrums. In addition, it is evident from these figures that the wave form of a rock noise is very complex. The wide frequency variation, 50 to 7500 Hz, is due to many variables; the effect of travel distance is the only one examined in this study. The higher frequency components of the wave are rapidly absorbed with distance or increasing travel time. Fig. 4 shows the change in waveform resulting from an additional travel distance of 195 ft. From these data, it is apparent that a resonant-type microseismic geophone cannot respond to all frequencies generated by a rock noise, and in spite of the fact that the tuned geophone is more sensitive at resonance, a geophone with less sensitivity but broader band width is much more effective in detecting rock noises. In addition, a study of broad-band microseismic records shows that both P and S-wave arrivals are easily detected, as shown in Fig. 5. All records analyzed to date show that most of the energy is in the S portion of the wave; hence, microseismic geophones should be well

Jan 1, 1970

By Bernard Schneider

The diversity of methods available to engineers and geologists for studying rock masses is a reflection of the fact that, despite the rapid and encouraging progress made over the last few years, there is still no unified and comprehensive method which can be used to predict the over- all behavior of a foundation. Nevertheless, it is agreed that the fundamental characteristic affecting the engineering properties of rock is fissuration, and this paper de- scribes a few new or improved methods of studying fissuration and its influence on major engineering factors such as permeability, deformability, or internal stresses in the rock volume. TESTS ON SAMPLES Conventional tests on samples using thin slices can be improved by staining the slices before cutting with certain ionic dyes which have an affinity for certain types of surface. This shows up the microdiscontinuities. For example (quoted terms are French trade names) : "Turquoise Motylhne JSA" will show up porous alteration of basic feldspars. "Vert brillant SA" is used for acid feldspars. "Fushine ASA" will show up voids in all rocks. A mixture of "Turquoise" and "Rhodamine BSA" will show up zones of alteration in all types of feldspars. With this technique, it is easy to make an optical classification of the different structural types, e.g.: (1) rocks completely free from voids; (2) rocks with microfissures, which in turn can be subdivided into (a) rocks with microfissures secant to the mineral structure, (b) rocks with microfissures parallel to the mineral structure, and (c) rocks with ran-

Jan 1, 1970

By Jean A. Andre

In 1969 "Société des Mines et Fonderies de Zinc de la Vieille-Montagne" produced 221,000 tons zinc ingots and 22,000 tons zinc dust, thus rating highest on the world's zinc producer list. The Company's plant at Balen, Belgium, with an output of 135,000 tons electrolytic zinc is the most important one of this group; it is an integrated metallurgical zinc and lead unit with recovery of most by-products. The present paper describes the zinc production facilities. The roasting section includes four fluid bed roasters (total concentrates charged: 740 tpd) and two sulfuric acid having a corresponding capacity. Calcine is leached in a fully automated plant by a two-step continuous process. Leaching residues, mixed with lead furnace slag, are treated in a shaft furnace. The recovered zinc fume is leached separately. In the near future, the leaching residues are to be treated by a wet process, developed in the Company's own laboratories. Purification of solutions is accomplished in two steps: antimony and zinc dust are added in the first one, only zinc dust in the second one for removal of cadmium. Electrolysis cells are partly of a conventional type. A new type of cell configuration was put onstream in October, 1969, planned output 60,000 tpy. Main features of the new cell rooms are the fully automatic pulling, stripping and replacing of the jumbo-size cathodes (immersed area 2.6 m2). Zinc cathodes are remelted in induction furnaces followed by in-line automatic casting and stacking machines.

Jan 1, 1970

By Foster Fraas

Under a very high vacuum of 10-8 torr the transfer of terrestrial mineral beneficiation methods to the vacuum ambient of extraterrestrial locations such as the lunar surface was investigated. In the size range for the electro-static and magnetic separation of ores (minus 35 plus 150 mesh) there is no adhesion of particles produced by crushing and grinding due to the limited contact area, and for repeated contacts area size has a frequency of occurrence in accordance to the normal law. The photoelectric effect which is successful in separating a few minerals in an air ambient has a wider application in a vacuum, while the lack of air viscosity and sound transmission provides for high feed velocities and the adaptation of particle vibration to dispersion and grinding. Contact electrification is reversible upon return to atmosphere.

Jan 1, 1970

By D. F. Scott

"DEFINITION OF THE REGION AND ITS BOUNDARIESTHE REGION of Western Canada covered by this re-port lies between the Precambrian rocks of the Canadian Shield and the structurally deformed rocks of the eastern Cordillera, extending northward from the international border to the 60th parallel. It is some 487,000 square miles in area, with a total sedimentary fill of about 535,000 cubic miles0>. It includes parts of the prairie provinces of Manitoba, Saskatchewan and Alberta and the northeast corner of British Columbia and forms part of the geological region known as the Interior Platform, commonly referred to as the Western Canada Sedimentary Basin. The bedrock comprises carbonates and evaporites of Paleozoic age that lie on Precambrian crystalline rocks and are over-lain by a relatively thick blanket of Mesozoic and Tertiary elastic rocks. The nearly flat-lying bedrock, covered by a thick mantle of glacial drift, forms the Interior Plains physiographic province."

Jan 1, 1970

By M. L. Klohn

The Felder ore deposit is a 5,000,000-pound uranium deposit in the South Texas Coastal Plain. It occurs in the basal sand of an Oakville Formation (Miocene) alluvial system. The host sand is a carbonate-rich arkose which contains virtually no carbonaceous debris and has been reduced by the local introduction of hydrogen sulfide. The ore lies well within the reduced zone and occurs as coffinite and uraninite that fill interstices and coat and replace grains. The overall geometric configuration of the ore is that of a winged, crescentic ore roll. Weak mineralization extends the wings of the ore roll and gives greater expression to the roll character. Departures from the shape are controlled by discontinuities in bed- ding and by proximity of the ore to the surface. Associated with the uranium is a broad halo of anomalous molybdenum. Subsidiary mineralized trends suggest a pre-existing up-dip position for the main roll. Oxidation from the surface largely destroyed this previous roll by solubilization of uranium. Uranium subsequently migrated into favorably reduced sand and reprecipitated at the present roll position.

Jan 1, 1970

By Pervez Patel, Martin G. Frohberg, Demetrios Papamantellos

Model experiments were carried out on the mass transfer of iodine between n-hexane and a 4 2 X 10-3 M aqueous sodium hydroxide solution. The influence of mechanical stirring by means of small gas bubbles (ca. 0.01 ml in volume) on mass transfer was examined in independent experiments. The results were described with the help of the penetration theory and in the case of bubble stirring with the help of a mathematical model based on this theory. S LAG-METAL reactions, especially those in steel-making processes, often occur under conditions where gas is evolved in the form of bubbles that break through the slag-metal interface. It is known that stirring by means of bubbles increases the mass transfer coefficient, but there has been very little quantitative work done in this field. Because of the difficulties that attach to experimental work at high temperatures this study was confined to model experiments at room temperature. EXPERIMENTAL APPARATUS The transport of iodine from an n-hexane layer into a weak sodium hydroxide solution was studied a) with stirring by means of bubbles and b) with mechanical stirring. The apparatus for the experiments with bubbles consisted of the cell, two Dreschel bottles filled with hexane in order to saturate the nitrogen flow, one flow meter, and a nitrogen gas cylinder fitted with a fine-regulating valve. Fig. 1 shows the cell consisting of a glass cylinder 33 cm in height with an overall diameter of 7.5 cm embedded in a copper flange. The flange is connected to a Plexiglas plate and to the gas inlet. The Plexiglas plate has holes of 0.2 mm diam bored into it which are spaced 1 cm from each other. For the experiments with mechanical stirring the bottom of the cell was sealed off by a Plexiglas plate. The upper layer was stirred by means of a glass stir-rer and the bottom layer with the help of a magnetic stirrer in a counter rotatory direction. Both stirrer speeds could be varied continuously. EXPERIMENTAL PROCEDURE Iodine dissolves in n-hexane producing a stable violet color thus enabling the iodine concentration in

Jan 1, 1970

By G. J. W. Kor, F. D. Richardson

The sulfide capacities a1 1500°C of slags in the systern CaO + CaF, +Al2O3 have been measured by bringing samples into equilibrium with gas mixtures made from CO + CO2 + SO, + N2. The capacities are negligzble both JOY CaF, and CaF, + Al2O3 melts but when lime is present even at 20 wt pct capacilies as high as 30 x lom3 can be obtained. The results have yielded information concerning the liquidus at 1500°C and fluoride-oxide melts in general. The slags used in electroslag refining contain substantial amounts of calcium fluoride. Robinson and Grainger' report that good results can be obtained by using slags of the approximate composition 70 wt pct CaF2 + 30 pct Al2O3. It has also been reported2 that a mixture of 50 pct CaF2 + 30 pct A12O3 + 20 pct CaO makes a good slag for general use. In view of the fact that very low sulfur contents are claimed for ingots produced by the electroslag process. studies have been made of the sulfide capacities [c, = wt pct S (PO2/Ps2)1/2 at 1500°C. of slags consisting of pure calcium fluoride, and of its mixtures with lime and/or alumina. These studies have also provided information on the phase diagrams. The slags were brought into equilibrium with gas mixtures prepared from NZ + CO + CO2 + SO2. Because CaFz is volatile and also easily hydrolyzed. measurements were made of its loss in weight in various flowing gas mixtures. EXPERIMENTAL Procedure. The apparatus and procedure were the same as described previously. Both platinum and iridium crucibles were used (height and inner diameter about 1 cm), but those made from iridium were stronger and able to withstand a greater number of experiments. In each experiment two crucibles were set in an alumina support and 1 g of slag mixture was divided between them. The materials from each crucible were analyzed separately after being brought to equilibrium with the gas, and then quenched in the water-cooled end of the reaction tube. Materials. Alumina and lime were prepared as de-scribed previously.4 Calcium fluoride was obtained by igniting Analar calcium fluoride in a platinum boat at about 800°C in a stream of pure dry nitrogen: the product was cooled in a desiccator. The slags were produced from mixtures of the powdered constituents, these being melted together in the course of each equilibrium experiment. The sulfur analyses and the X-ray diffraction meas- urements on the solidified slags were made as described previously.4 From the latter it appears that the CaF2 contained less than 0.5 mol pct CaO. RESULTS Values of (ps2/po2) for the Gas Mixtures. The re-sults have been represented in terms of (ps, /Po,)"? for the various gas mixtures used. The va1;es of this function at 1500°C are listed in Table I: they were calculated from the data cited previously for calculations at 1350°C 4 Weight Losses with CaF, and CaF, + CaO. The re-sults of the weight loss measurements* at 1500°C for

Jan 1, 1970

By Klaus Emicke

The paper describes the lead refining process operated at Norddeutsche Affinerie (N.A.). Incoming materials are different grades of lead with varying percentages of impurities: Cu, Te, As, Sn, Sb, Bi, precious metals. The facilities are designed for charge-wise operation. After drossing, generally Te, As, Sn and Sb are removed substantially by the Harris Refining Process using fused NaOH. A certain selectivity during refining is achieved by controlled addition of NaNO3. Another refining step is decopperizing by means of elemental sulfur. Complete separation of Te, As, Sn and Sb is accomplished by chemical methods in a leaching plant. A Howard Press is used in the Parkes Process for desilverizing. After vacuum dezinking in kettle, Bi is removed, if required, by means of Ca and Mg. In an end refining step Ca, Mg and Zn are removed by having the lead melt treated with NaOH and NaN03. The refined lead as such, or in the form of special alloys, is cast by an ingot casting machine into 50-kg ingots. Zinc which is used as a precipitant in the Parkes Process is recovered by distillation from the high grade Ag-Zn-Pb crystals in Faber du Faur retorts while the Pb/Ag alloy is fed to the cupellation furnace. Ca and Mg are removed from the Ca-Mg-Bi crystals formed in the course of Bi removal, and the Bi-bearing lead is cast into anodes. The electrolytic lead refining facilities at N.A. are operated largely for the purpose of separating Pb and Bi. These facilities are also used particularly for the refining of Bi-bearing lead which had gone through the above process, but from which Bi has not been removed by Ca and Mg.

Jan 1, 1970

By W. R. Wilcox

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

Jan 1, 1970

Jan 1, 1970

By C. C. Harris

The 3-parameter equation* was introduced1 as having the necessary form and flexibility for describing the major features of size distribution curves. Also, Eq. 1 was shown to contain most of the widely used 2-parameter equations as special cases. Special methods are necessary in order to determine the parameters of 3-parameter equations by graphical means. The procedure given previously required double graphical interpolation followed by regraphing the interpolated data. The theoretical basis of the method was a difference equation eliminating y. Several other methods for obtaining the parameters have been under development and one method appears to overcome the disadvantages of the earlier method and satisfies several procedural requirements. The points in favor of the new method as compared to the earlier method are as follows: 1. Estimation of the quality of fit is direct, and is in fact an essential part of the procedure. 2. The data is plotted directly without the necessity of interpolation from a graph. 3. The method makes use of Rosin-Rammler2 paper which because of expanded scaling in the coarse sizes leads to improved accuracy1 as compared with the log-log plot for the Gates3-Gaudin4-Schubann5 representation. 4. There is a gain over the earlier method in overall accuracy and in simplicity.

Jan 1, 1970