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By K. W. Smith, E. A. Thomas

Various grades of synthetic mullite have been developed in recent years to replace or supplement natural sources of mullite deriued from the mullite group of minerals consisting of sillimanite, kyanite, and andalusite. Raw materials and heat treating processes used in making synthetic mullite are described. Chemical and physical data are given for typical grades and crystalline structure is illustrated with micrographs. Use of synthetic mullite as a refractory material in the glass and metallurgical industries is discussed. Mullite (3A12O3.2siO2), the only stable compound formed in the alumina-silica system, is usually present to some degree in all aluminum silicate ceramic products. The formation of mullite is considered beneficial to give rigidity to the structure and is dependent upon the ratio of Al2O3 to SiO2 in the original composition, particle size, degree of mixing, firing temperature, cooling rate, and the presence of auxiliary glass-forming fluxes. Mullite may also be formed at the reaction interface of fire clay or alumina-type refractories in contact with glass or slag melts. The term synthetic mullite is commonly used today to identify a class of sintered and fused aggregates or grains in the alumina-silica system having a highly developed mullite structure but derived mainly from raw materials other than the sillimanite group of minerals. Within the past 15 years extensive research has been done to develop economical processes to form sintered synthetic mullite aggregate to replace calcined Indian kyanite in super-refractories. Severa1 brands of such mullite are now being produced in commerical quantity and finding extensive use in refractories. Based on the service results of such refractories in many applications throughout the metallurgical, ceramic, and glass industry these developments have been considered successful and suitable substitutes for Indian kyanite now appear assured. EARLY DEVELOPMENT The conversion of kyanite, sillimanite and anda-lusite minerals of the sillimanite group to mullite and their use in refractories and porcelain have been discussed quite extensively in the literature by peck,' Grieg,' Riddle and Foster,3 Bowen and Grieg,4 and others and will only be mentioned here for reference to compare properties with synthetic mullite. In 1928, curtis5 reported on the development of a high temperature gas-converter process for forming synthetic mullite. The raw materials were derived mainly from lumps of high alumina clay of the correct natural composition or blends of clays and alumina that was interground and briquetted to form a suitable charge to maintain a surface combustion firing within the converter. Curtis was, no doubt, the first to illustrate by micrographs in natural color the crystalline structure of mullite derived from kyanite and mullite derived by sintering clay and alumina mixtures at temperatures above cone 32 (3123°F) and by electric fusion. In 1937, sei16 was issued a patent covering the use of a mixture of alumina-silica minerals and alumina in the proportion to form a mullite-yielding material at temperatures in excess of 3100' F. During the period from 1930 to 1940, economic conditions were not favorable for the production of synthetic mullite mainly due to an adequate supply of good grades of Indian kyanite ore suitable for conversion to mullite. Uncertain conditions on availability of the Indian kyanite during the early stages of World War II fostered further study on the development of synthetic substitutes. In 1943, McVay and wilson7 reported on an extensive investigation of domestic substitute materials. Their work covered essentially the use of mixtures of electric furnace mullite, calcined topaz, and calcined domestic kyanite. Compositions were found that gave equivalent or better hot load strength than Indian kyanite in mullite-type brick compositions; however, the calcining of the topaz presented certain physical and chemical problems on the disposition of silicofluoride and hydrofluoric acid while the high cost of electric furnace mullite was a limiting factor. In this work it was pointed out that water-quenched fused mullite was found to be unstable on reheat and gave poor hot load strength due to excessive glass present whereas the slow cooled or annealed mullite contained large crystals of mullite and corundum with little glass and gave superior results.

Jan 1, 1961

By Edward Keller

THE ASSAY FOR COPPER. SOMEONE some time ago remarked that some chemists still insist on telling us how to determine copper by the electrolytic method. The. writer must confess that he believes that everything is not known definitely as yet as to how the exact amount of copper is determined in such material as purest commercial electrolytic copper. Some of us are not yet convinced that the pure copper atom is at all times deposited from an acid solution and that no oxygen or hydrogen will, under certain conditions, accompany it. Difficulties with impurer material are frequent, but erroneous results are not always apparent, since these do not speak so readily for themselves as those in the first case. By this is meant that if a chemist finds 100 per cent. of copper in electrolytic copper it is pretty certain that he perceives the result to be wrong, while if he finds 0.1 per cent. of copper too much in a very impure material he is far more likely to be unconscious of his error. These, in a wide experience, are frequent happenings and the writer has always looked with interest to publications on this subject. In turn, he :feels justified in giving to others a few of his own observations. Up to a few years ago there were two methods of electrolytic copper assay in technical use, which had in common, that the amount of copper deposited on the cathode did not exceed 2 g., and they differed in that, for the one a large sample 1 (20 to 80 g.) was taken from the general sample by a splitting device, dissolved, and from the solution a small portion (to contain 1 or 2, g. of copper) measured out for the electrolytic deposition; in the other Method the copper was determined, generally in 1-g. portions of the separated coarse and fine portions of the sample, all of which passed -a 16 or 20-mesh screen, being accomplished by a 40-mesh screen,

Jan 8, 1913

By A. J. Griest, P. D. Frost, H. A. Robinson

The flow characteristics and uniform elongation of alpha-beta titanium alloys in the solution-treated condition were shown to be markedly affected by the solution temperature. Two classes of alpha-beta alloys were distinguished, based on the effect of solution temperature on the uniform elongation. Martensitic alpha-beta alloys, which are relatively weakly beta-stabilized, showed decreasing values of uniform elongation as the solution temperature was initially increased. However, after solution-treatment at still higher temperatures in the alpha-beta field, the uniform elongation of these alloys was again high, and often attained its maximum value. Nonmartensitic alpha-beta alloys, which are more heavily beta-stabilized, showed a continuous decrease of uniform elongation with increasing solution temperature. The behavior was rationalized in terms of the alpha-beta ratio and the alloy content of the beta existing at the solution temperature. The data indicate that in commercial practice close temperature control may be required to get maximum uniform elongotion, and hence, maximum potential formability, in solution-treated sheet. Bend-test data also were obtained for the solution-treated conditions. A MOST important objective of current titanium research is the development of age-hardenable alloys with superior formability in the solution -treated condition. Alpha-beta titanium alloys have been shown to be amenable to high-strength aging treatments after solution-treatment in the alpha-beta field.' However, heat-treatment data on the properties of solution-treated sheet, such as uniform elongation, minimum bend radius, and flow properties, which have a bearing on the potential formability, have not been widely available. This paper presents only the most significant results of a research program conducted at Battelle for the Air Force in an effort to develop sheet alloys that can be formed readily as solution-treated and subsequently aged to very high strengths. Data for 10 compositions representative of the more than 25 alloys studied in this program are presented. A primary objective of the paper is to demonstrate the pronounced dependence of the flow characteristics and uniform elongation on solution-treatment temperature. This effect is believed to be vitally important in the commercial heat-treatment of age-hardenable titanium sheet alloys. Experimental Procedures Melting and Fabrication—The nominal and actual compositions, beta transi temperatures, and rolling temperatures of 10 of the 30 alloys studied are presented in Table I. Stock :€or two of the alloys, E (Ti- 8Mn) and J (Ti-6A1-4V) was obtained from commercial heats. The remaining heats, except D and I, were double melted as 10-lb heats in a consumable-electrode furnace. Melting stock was 120 Brine11 hardness sponge. The oxygen and hydrogen analyses spotted throughout the heats indicate the range of interstitial levels resulting from the melting practice used. Heats D and I were melted as 20-lb ingots with the same grade of sponge. These ingots were cut in half and one portion used in the present evaluation. The ingots, which were about 4 in. diam and 4 in. in height, were upset forged and drawn at 1750°F to sheet bar 5/8 in. thick by 2 1/2 in. wide in such a manner that the top of the ingot corresponded to the top of the sheet bar. Slabs of the sheet bar, 5 1/2 in. in length were scalped to 1/2 in. thickness and rolled at the temperatures indicated in Table I to approximately 0.055 in. sheet. Elongation during rolling took place at 90" to the original forged length. The fabrication procedure used is described in some detail since the experimental heats showed considerable directionality in mechanical properties. The rolling procedures for the commercial heats were unknown, but were such as to produce essentially isotropic properties. All heats, as rolled, showed microstructures typical of alpha-beta alloys worked in the alpha-beta field; that is, the structures consisted of equiaxed alpha particles in a beta matrix. Heat Treatment— The effects of solution and aging heat-treatments on the properties of the alloys were evaluated uSing longitudinal and transverse tensile and bend coupons sheared from the sheet. Two or three solution-treated conditions were evaluated for each alloy. In addition, the alloys were also tested after annealing at 1200°F for 4 hr and furnace cooling. The solution-treated and annealed conditions were those in which the alloys might be expected to

Jan 1, 1959

By D. C. Hilty, W. Crafts

J. Chipman—It has been my privilege to discuss this work with the authors on several occasions and to observe at first hand the experimental methods employed. I wish, therefore, to emphasize certain points which they have mentioned only briefly with regard to the experimental techniques. The rotating induction furnace as here employed interposes liquid metal between slag and refractory thus preventing the two nonmetallic parts of the system from reaching equilibrium with one another. It is therefore impossible for the metallic phase to be completely in equilibrium with both the slag and the crucible. The metal also acts as a partially permeable membrane allowing certain components, including oxygen, to diffuse from slag to crucible. This transfer results in building up on the face of the crucible a layer of material whose composition is in part dependent on that of the bath. Reactions between the layer and the solid refractory are slow, as evidenced by the rather good life of the crucible. Hence it seems probable that the layer is more nearly in equilibrium with the metal than with the underlying crucible material and that, once it is established under a bath of a given composition, its further reactions with that bath are slow. Additions to slag or bath may be followed by changes in the layer; and time must be allowed for virtual completion of such changes, before it can be assumed that slag and metal are in equilibrium. We may judge from the results reported that, in general, this was the case and that the data represent at least quite close approximations to slag-metal equilibrium. Data on deoxidation and on oxygen solubility are no better than the analytical methods employed. The vacuum fusion method as used by the authors seems entirely adequate for the samples analyzed. I have had frequent occasion to compare results with their laboratory, always with very satisfactory agreement. The determination of aluminum at very low concentrations is perhaps an even more difficult procedure. Here also the colorimetric method used has been worked out with great care and is undoubtedly the most dependable method available. The discrepancy between observed and calculated deoxidation or solubility lines is not to be explained as the result of experimental errors, either in the sampling or analysis of the metal. Nor is it to be blamed upon inaccuracies in the several kinds of indirect data upon which the calculated results were based. It is true that both the observed and the calculated lines admit of some uncertainty as to their exact locations, but the uncertainties are small compared to the wide gap which separates the two lines. The authors have pointed out the real cause of the discrepancy. In all of their experiments the solid phase was not Al2O3 but a mixed oxide containing iron and aluminum. This suggests an extension of the calculated values to include equilibrium with the spinel FeO . A12O3. The free energies of FeO and A12O3 are known, that of the spinel is not. However, it cannot differ greatly from that of its component oxides for even in the more stable spinel, chromite, the free energy of formation from the oxides is less than 10,000 cal. For purposes of calculation we shall call this free energy X and solve for values of X lying between zero and 10,000 cal. The other data required are taken from the forthcoming revision of "Basic Open Hearth Steelmaking" and are given in the following equations in which underlined symbols indicate elements dissolved in liquid steel and the standard concentrations are 1 pct. ?F° at 1600°C, cal ?LA = 2 Al + 3 O; + 107,200 FeO = Fe + 0; + 5,460 FeO + A12O3 = Fe + 2A1 + 4 0; + 112,660 — X The corresponding equilibrium concentrations are shown in fig. 21. The line marked A12O3 corresponds to the first equation, those marked FeO . AL2O3 correspond to the last, with X = 0, 5000 and 10,000 cal, respectively. The two upper lines represent the data of Hilty and Crafts and of Wentrup and Hieber. The points are the observations of Hilty and Crafts in the presence of 0.50 pct Mn.

Jan 1, 1951

By David T. Peterson

Calcium metal was found to deoxidize thorizcm at 1000° to 1200° C. The reaction kinetics were determilled and related to the diffusion coefficients of oxygen in thorium. The solubility of oxygen in thorium, the minimum oxygen concentration, and the diffusion coefficient were determined from 1000° to 1200°C. This firocess results in the lowest oxygen concentrations zohich have been reported for thorium metal. FOR many years it has been known that calcium metal will reduce thorium oxide to thorium metal. This reaction has been the basis for several methods of preparing thorium metal. From the equations giv-by Kubaschewski and vans, ' AF" for the reaction Cao, + Tho,(,) - CaO(,, + Th(,) was calculated and found to be -3.4 kcal at 1000°C, -2.5 kcal at llOO°C, and -2.0 kcal at 1200°c. Thorium is very slightly soluble in liquid calcium, and the solubility of calcium in solid thorium is very low. Consequently these metals would be in essentially their reference states. If thorium containing oxygen were equilibrated with liquid calcium between 1000° and 1200°C, the oxygen content of the thorium would have to be below the solubility limit in thorium. Oxygen is one of the impurities most difficult to remove from thorium and is the most abundant impurity in metal prepared by almost all known methods. Fortunately, oxygen does not have a large influence on the properties of thorium because the solubility in solid thorium is very low. EvenT in thorium containing 100 ppm of 0, particles of thorium oxide can be observed in the microstructure. In view of the incompatibility of thorium oxide and liquid calcium and the low solubility of thorium oxide in thorium, the deoxidation of thorium by this method was investigated. For thorium containing an amount of oxygen well in excess of the solubility limit, the reaction should proceed in the following sequence. The oxygen content of the thorium matrix near the surface would be depleted by the diffusion of oxygen to the surface. At the surface, the oxygen would react with calcium to form calcium oxide. To maintain equilibrium within the thorium, thorium oxide would dissolve to keep the matrix saturated. Consequently, the thorium-oxide particles would disappear first at the surface and then the particle-free rim would grow in thickness. If the rate-controlling step were the diffusion of oxygen through this layer of thorium which was growing in thickness in direct proportion to the amount of oxygen removed, the well known parabolic time law should be observed. If the oxygen concentration at the surface of the thorium and at the inner surface of the deoxidized rim were known, the diffusion coefficient of oxygen in thorium could be calculated from the parabolic rate constant. EXPERIMENTAL PROCEDURE The thorium metal used in this study was prepared by calcium reduction of ThF, by the method described by Wilhelm.' The analysis of this metal is given in Table I. The carbon was determined by combustion, the oxygen by the HC1-insoluble residue method, nitrogen by the Kjeldahl method, and the other elements by emission spectroscopy. A section of this ingot was hot rolled at 600°C to 1/4 and 1/8-in. thick plates. Specimens approximately 7/8 in. square were cut from these plates, and all surfaces of the specimens were cleaned and smoothed by filing with a clean file. Individual specimens were placed in 1-in. diam by 2-in.-long tantalum capsules. Approximately 1 g of clean, high-purity calcium was placed in the capsules and an end closure arc-welded in place. The tantalum capsules were sealed in Inconel crucibles to protect the reactive metals from oxidation. The entire loading procedure was done in a glove box filled with pure argon. The loaded crucibles were placed in a muffle furnace, controlled within 2OC of the desired temperature, for a measured length of time. After the specimen had cooled to room temperature, it was sectioned perpendicular to the large faces and through the mid-point of two of the sides. The sectioned specimen was mounted and polished through Linde A abrasive. The rim which was free of thorium-oxide particles could be clearly observed microscopically as mechanically polished. Twenty measurements of the thickness of the rim were made at equally spaced points far enough from the end of the

Jan 1, 1962

By Paul B. Crawford, Bobby L. Landrum

An electrical model study has been mode to estimate the effect of horizontal fractures in thick reservoirs on pattern conductivity. For the patterns studied, it is shown that fracturing all the wells in the pattern in-creases the conductivity considerably more than frac-turing only single wells. For certain conditions one large fracture is more effective in increasing conductivity than several fractures of half the radius. Particularly in thick reservoirs and with large fractures, the center of the pay is found to be more responsive than other locations. For the seven-spot pattern fracturing the center well is more effective in increasing pattern con-ductivity than fracturing all outer wells with fractures of the same size. INTRODUCTION Although commercial fracturing has been used for some time very little quantitative information is known about the effects of fractures on reservoir behavior. The purpose of this work was to estimate the effect of horizontal fractures in thick reservoirs on the con-ductivity of various flooding and cycling patterns.2 Circular fractures originating at the wellbore and extending symmetrically into the pay were considered. ANALYSIS Electrical models were used in making this study. Horizontal fractures were simulated by copper sheets shaped like the fractures and of a proportional size; the wellbore was simulated by a copper wire. A dilute salt solution served as a conducting medium. A con-ductivity bridge was used to measure the conductivities of the various patterns studied. EFFECT OF HORIZONTAL FRACTURES ON CONDUCTIVITY Fig. 1 shows the effect on square and staggered line drive patterns of horizontal fractures located in the center of the pay. The model is shown schematically in the insert. The upper and lower groups of lines show the effect on conductivity when all wells are fractured, and when only one well is fractured, respectively. In general, pattern conductivities are substantially improved by fracturing all wells. Fig. 2 shows the effect of multiple horizontal frac-tures on the conductivity of a line-drive pattern. At

Jan 1, 1958

By Wolfgang Gartner

METALLURGISTS engaged in the pulling of single crystals of germanium and silicon, and their zone purification and zone levelling for transistor and diode production, have found that the lifetimes of minority carriers in low resistivity samples tend to be shorter than in high resistivity material, although equal care is taken in the crystal preparation. In other words, it is more difficult to obtain long lifetimes in single crystals of low resistivity semiconductors. It is the purpose of this note to point out that this phenomenon follows directly from the Hall1 and Shockley-Read' theories of lifetimes in semiconductors." In general, the recombination mechanism may be very complicated,' but experiments seem to indicate that the simple formula2 for the lifetime of excess carriers given by n0 + n3 Pn + P1 T = Tpo,------------------+ Tjpu ----------------------- [ 1 ] nu + pn na+ + Pa is a good representation of the situation prevailing in transistor grade semiconductors. In this formula, no and pa are the equilibrium densities of electrons 6+ - E./ET and holes, n1 = N,e is the number of electrons E1- E2/KT in the conduction band, and p1 - N,e is the number of holes in the valence band, both for the case in which the Fermi level falls at the trap level, E1. N,. is the effective density of states in the conduction band; E1, the recombination level; E1, the lower edge of the conduction band; k, Boltzmann's constant; T, absolute temperature; N,., effective density of states in the valence band; and E,., the upper edge of the valence band. t,.,, denotes the lifetime of holes injected into highly n-type material, and The indicates the lifetime of electrons injected into highly p-type material. Eq. 1 holds for nondegenerate semiconductors in which only one recombination level is active and the charge in the recombination centers is neglected. It is further assumed that the number of injected ex-

Jan 1, 1957

By R. J. Wasilewski

Electrical resistivity variation with temperature was measured on a series of alloys containting up to 33 at. pct of oxygen over the range 77° to1500°K. The resistivity behavior is highly anomalous and itzconsistent with simple metallic conduction. Both composition and temperature-depended resistivity singularities were observed. A few experiments carried out on Ti-N and Zr-O alloys indicate the presence of similar anomalies. These observations, together with the published data on effects of substi-tutional alloying on the resistiuity of titanium, suggest that the anomalies are inhevent in the electron structure of this group oj metals. The existence of two-band conduction, and a significant shift of bands relative to each other with temperature and/or the electron concentration are suggested. CONSIDERABLE advances have been made in recent years in the alloy theory of simple metals. Very little, however, is known about the bonding in transition metals and their alloys.&apos; Titanium, with its relatively few electrons, may be expected to show simpler alloying behavior than the more complex transition elements. Its alloys with the interstitial elements appear particularly attractive in an investigation of bonding characteristics because of a) the simple nature of the solute elements, b) the remarkable similarity between the equiatomic structures Tic, TiN, and TiO, and c) the extensive solid solubility ranges of oxygen and nitrogen in a titanium reported.2,3 The Ti-O system was chosen for the most extensive investigation because of the relative ease of preparation of suitable specimens. Since the main object of the work was to obtain data on the bonding and its changes on alloying, electron-sensitive properties were primarily investigated. The present work describes the investigation on the electrical resistivity-temperature-oxygen content relationships. A few experiments were also carried out at selected compositions in the Ti-N and Zr-O systems. EXPERIMENTAL Materials and Method. Polycrystalline specimens were prepared in the form of hairpin strips some 50 by 5 by 0.15 to 0.50 mm by direct metal-gas reaction. This was carried out by controlled oxidation followed by a homogenizing anneal at a higher temperature. All the test specimens were fully homogenized as judged from the uniform microstructure and microhardness. To avoid preferred orientation, each strip specimen was annealed in the ß range prior to the oxidation, this procedure assuring random orientation in the strip;4 hence any texture resulting from the oxidation reaction itself affected all the specimens to a similar extent. Titanium used was of high purity (66 DPN, 10 Kg load; major impurities 0,-43G ppm, N,-70 ppm, C-25 ppm, Fe-14G ppm). The solute content of the alloys was determined by weighing, after the reaction with a known amount of oxygen. The specimens in which the discrepancy between the volumetric and gravimetric measurements exceeded 2 pct (or 0.2 mg for the low oxygen alloys) were rejected. The mean between the two measurements was then taken as the oxygen content of the alloy. Check analyses showed no measurable nitrogen contamination. All oxygen contents are given in atomic percent. Zr-O alloys were prepared in identical manner from hafnium-free crystal bar metal, cold-rolled to strip 0.25 mm thick. Ti-N alloys required very long reaction times at the maximum temperature available (1250°C). In order, therefore, to detect possible oxygen contamination, duplicate specimens were reacted in every experimental run, and one of these was analyzed both for oxygen (vacuum fusion) and for nitrogen (Kjeldahl). Only the specimens in which the check analysis showed < 1000 ppm O were then used for resistivity investigation. Since only relatively high nitrogen alloys (7.1 at. pct; i.e., 2 wt pct N,) were investigated, this oxygen contamination was considered permissible. Dc resistance was measured by the four-probe method as previously described.= The temperature was determined with a calibrated thermocouple placed in the center of the specimen hairpin. The errors in the specimen resistance values thus obtained were estimated at 1 pct due almost exclusively to the finite thickness of the potential wires and the consequent uncertainty as regards the true resistance length of the specimen. For the calculation of the specific resistance, however, no dimensional measurements could be carried out on most of the

Jan 1, 1962

1. Any society of undergraduates at a technical school, comprising students in any branch of engineering, metallurgy, chemistry, geology, etc, may be recognized by the Board of Directors in its discretion as an Affiliated Student Society, and its name, to¬gether with the names of its president and its secretary, may be published in MINING AND METALLURGY or the DIRECTORY of the Institute. The members of such a society will not be named individually on the membership list of the Institute, but may at any time be proposed for election as associates or junior associates of the Institute, in the usual way. 2. Membership in an Affiliated Student Society, certified by the official representative thereof, and accompanied by suitable testimony as to character and qualifications, will have special weight with the Membership Committee of the Institute, in its consideration of the proposal of a candidate for membership. The Affiliated Student Societies receive the following privileges: 1 A copy of MINING AND METALLURGY free; 2. The use of Employment Service; 3. The use of MINING AND METALLURGY for publicity purposes, such as printing notices of their activities, etc ; 4. Assistance in obtaining speakers for their meetings, lists of moving-picture films, etc. To retain the privileges of the Affiliated Student Society, its officers must keep in touch with the Secretary of the Institute and advise him of its activities. The foregoing plan is not confined to students in mining engi¬neering or metallurgy. Any undergraduate society of engineers may avail itself of the privileges offered. Societies desiring to be recognized as Affiliated Student Societies are requested to make application to the Secretary of the Institute, giving particulars as to their nature, membership and officers. The accompanying list gives the names of the Affiliated Student Societies as of April 15, 1927, and their presidents and secretaries, in so far as they have been reported to the Secretary of the Insti¬tute.

Jan 1, 1923

By O&apos, R. G. Meara, B. W. Gandrud

In 1034 the Southern Experiment Station of the U.S. Bureau of Mines in cooperation with the University of Alabama began an investigation of the availability of kyanite ores as a source of raw material for the manufacture of refractories. Under this program, gravity concentration and flotation tests have been made on two varieties of Georgia kyariite ore, mica schist and massive. Most of the attention has been directed to the mica schist ores, as they are more widely distributed and seem to offer greater economic possibilities than the massive ores. It is evident that the preparation of kyanite for use as a refractory material involves other considerations than the mere elimination of impurities. A concentration process that eliminates impurities satisfactorily may have to be followed by some additional treatment, since the final product must be of a coarseness and size ratio that will make it suitable for refractories manufacture. So far in the investigation at the Southern Experiment Station of the U.S. Bureau of Mines only the concentration problem has been considered, and this paper is intended as an interim report. Ores The schist ores contain 1 to 9 per cent of kyanite crystals embedded in mica and quartz, with smaller amounts of graphite, garnet and iron oxide and minor amounts of other heavy minerals. The garnet content varies from a trace to a few per cent. The minerals are easily released by moderate grinding. The size of the kyanite ranges from fine needles to crystals 1 1/2 in. long, 1/2 in. wide and 1/4 in. thick. The garnet, quartz and iron oxide grains have a smaller mean mesh than most of the kyanite. The maximum size of the garnet crystals corresponds to about 14 mesh and that of the sand grains is considerably less. Most of the iron oxide is still finer, for the minus 100-mesh size is greatly enriched in Fe²O3. The massive ore consists of radiating masses of kyanite interlocked with quartz, mica, corundum and small amounts of other heavy minerals.

Jan 1, 1938

By B. W. Gandrud, R. G. Meara, O&apos

In 1034 the Southern Experiment Station of the U.S. Bureau of Mines in cooperation with the University of Alabama began an investigation of the availability of kyanite ores as a source of raw material for the manufacture of refractories. Under this program, gravity concentration and flotation tests have been made on two varieties of Georgia kyariite ore, mica schist and massive. Most of the attention has been directed to the mica schist ores, as they are more widely distributed and seem to offer greater economic possibilities than the massive ores. It is evident that the preparation of kyanite for use as a refractory material involves other considerations than the mere elimination of impurities. A concentration process that eliminates impurities satisfactorily may have to be followed by some additional treatment, since the final product must be of a coarseness and size ratio that will make it suitable for refractories manufacture. So far in the investigation at the Southern Experiment Station of the U.S. Bureau of Mines only the concentration problem has been considered, and this paper is intended as an interim report. Ores The schist ores contain 1 to 9 per cent of kyanite crystals embedded in mica and quartz, with smaller amounts of graphite, garnet and iron oxide and minor amounts of other heavy minerals. The garnet content varies from a trace to a few per cent. The minerals are easily released by moderate grinding. The size of the kyanite ranges from fine needles to crystals 1 1/2 in. long, 1/2 in. wide and 1/4 in. thick. The garnet, quartz and iron oxide grains have a smaller mean mesh than most of the kyanite. The maximum size of the garnet crystals corresponds to about 14 mesh and that of the sand grains is considerably less. Most of the iron oxide is still finer, for the minus 100-mesh size is greatly enriched in Fe²O3. The massive ore consists of radiating masses of kyanite interlocked with quartz, mica, corundum and small amounts of other heavy minerals.

Jan 1, 1938

By F. E. Crane, H. A. Kendall, G. H. F. Gardner

Two effects of a difference in density may be observed in miscible displacement. As the difference is increased from zero there is first a change in mode from multiple fingers to a single finger. A further increase results in a more rapid growth of the single finger. Miscible displacement with multiple fingers has been discussed by Blackwell, et al, whereas miscible displacement with a single finger has been discussed by Craig, et al. In the present paper experiments are described which bridge the gap between these extreme cases. INTRODUCTION Craig, et al,1 investigated the effect of gravity on frontal displacements for circumstances in which the gravity forces were significant. Blackwell, et a1,2 dealt with the other extreme in which gravity forces were negligible. The considerable difference between their results is illustrated in Fig. 1 where the breakthrough recoveries are plotted against the mobility ratio. The experiments described in the present paper were conducted to examine how the transition from the one extreme case to the other occurs when the gravity forces are gradually reduced. The transition is well illustrated by the production history after breakthrough. Fig. 2 shows how the number of pore volumes which must be injected at a constant rate to displace 98 per cent of the original fluid depends on the gravity force. For each mobility ratio there is a transition range, and a very significant change in the number of pore volumes occurs when this range is traversed. This range of the gravity force is physically linked with the formation of viscous fingers. A single finger is predominant for larger gravity forces; a multiplicity of fingers is formed for smaller gravity forces. Improved recovery and the occurrence of multiple fingers is concomitant with a large increase in the amount by which the fluids are mixed within the porous medium. The transition range depends on all the dimension-less groups which characterize the problem; but this dependence has not been exhaustively studied as yet and only fragmentary results are discussed in this paper.

By C. D Looker

Common salt is mentioned in the most ancient writings as an important article of diet. It is fairly certain that it was used by men and animals long before the dawn of civilization. Its presence in natural springs has often been the determining factor in colonization; wars have been fought for possession of salt deposits; trade routes have been established expressly for the purpose of traffic in salt. Naturally this led men into adventures and discoveries that altered history and advanced civilization. In the early days the uses for salt were few and the methods of manufacture were crude and the purity low when compared to salt of the present day. Then the salt came largely from springs, shallow wells or the ocean, while today deep wells must be drilled to the natural brines or beds of rock salt and spacious shafts sunk so that the ancient deposits may be made to yield their supply of stored mineral. Mining and Purification The quantity of available salt seems inexhaustible. It occurs in practically every country of the globe. About 20 million tons is produced and consumed annually in the world. Of this amount about 7 million tons is produced in the United States; 13/4 million tons of rock salt, 2 1/4 million tons as evaporated salt and 31/2 million tons in brine used in the chemical industry. Mined rock salt is used in its natural state without purification. It is classified for the trade by crushing and screening. The average purity of rock salt mined in the United States is about 98.3 per cent pure sodium chloride1. The usual impurities are gypsiferous shale, anhydrite and silica, with traces of potassium, magnesium and calcium compounds. Refined or evaporated salt is made by crystallizing the salt from brine in open pans or vacuum pans. A comparatively small amount of salt is made from ocean water or the brines of inland lakes or seas, sometimes by solar evaporation. By far the larger amount of brine is obtained by drill-

Jan 1, 1938

By C. D. Looker

Common salt is mentioned in the most ancient writings as an important article of diet. It is fairly certain that it was used by men and animals long before the dawn of civilization. Its presence in natural springs has often been the determining factor in colonization; wars have been fought for possession of salt deposits; trade routes have been established expressly for the purpose of traffic in salt. Naturally this led men into adventures and discoveries that altered history and advanced civilization. In the early days the uses for salt were few and the methods of manufacture were crude and the purity low when compared to salt of the present day. Then the salt came largely from springs, shallow wells or the ocean, while today deep wells must be drilled to the natural brines or beds of rock salt and spacious shafts sunk so that the ancient deposits may be made to yield their supply of stored mineral. Mining and Purification The quantity of available salt seems inexhaustible. It occurs in practically every country of the globe. About 20 million tons is produced and consumed annually in the world. Of this amount about 7 million tons is produced in the United States; 13/4 million tons of rock salt, 2 1/4 million tons as evaporated salt and 31/2 million tons in brine used in the chemical industry. Mined rock salt is used in its natural state without purification. It is classified for the trade by crushing and screening. The average purity of rock salt mined in the United States is about 98.3 per cent pure sodium chloride1. The usual impurities are gypsiferous shale, anhydrite and silica, with traces of potassium, magnesium and calcium compounds. Refined or evaporated salt is made by crystallizing the salt from brine in open pans or vacuum pans. A comparatively small amount of salt is made from ocean water or the brines of inland lakes or seas, sometimes by solar evaporation. By far the larger amount of brine is obtained by drill-

Jan 1, 1938

By Arthur C. Simmons

Oil production and activity in northern and central Pennsylvania was slightly less in 1939 than in the previous year, but owing to higher average prices 1939 was undoubtedly a better business year. The last quarter showed markedly increased activities throughout all of the Pennsylvania fields. Production, Stocks and Price Storage of Pennsylvania crude oil at pipe lines and refineries totaled 5,413,000 bbl. on Dec. 31, 1938, and declined during the year 1,124,000 bbl. to a total of 4,319,000 bbl. at the end of 1939. The stocks of crude at the end of the year represent the lowest point reached in Pennsylvania-grade crude storage in recent years. Stocks increased slightly during April, May and June, but decreased during all other months of 1939. The Bradford field production within the state of Pennsylvania averaged 35,340 bbl. per day throughout 1939, which represents a decrease of 1419 bbl. a day from the 1938 average. The production in central and southern Pennsylvania increased 1176 bbl. per day, averaging 12,159 bbl. throughout 1939. Table 1 includes annual production for the part of Bradford field situated within the state of Pennsylvania, for central and southern Pennsylvania, and for the entire state of Pennsylvania. A definite segregation of production between the Bradford field and central and southern Pennsylvania is slightly ambiguous because a portion of the oil from the newly discovered Music Mountain pool is included statistically in each area. In all probability the entire increase and some small addition to the production from southern Pennsylvania can be attributed to oil produced from the Music Mountain pool. Within the Bradford field, six price changes occurred throughout the year. At the beginning of 1939 the price of Bradford crude oil was $1.80 per barrel, whereas by the end of the year it had risen to $2.50. The weighted average price for Bradford crude during 1939 was $2.059 per barrel.

Jan 1, 1940

By Morris Cohen

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expression for the composition (d) of the liquid-to-solid transfer at each temperature has been derived: d = ZLXL(XL - P) + Zsxs(P- ZL(XL - P) + Zs(P - Xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, XL and xs are the composi-tions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under considera-tion. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d -versus-temperature curves for two alloys Pl and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid FIG. I.-GENERAL SOLID SOLUTION DIAGRAM SHOWING S CURVES FOR ALLOYS P1 AND P2. phase only at the temperature of the be-ginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate tem-perature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling, the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1940

By Arthur C. Simmons

Oil production and activity in northern and central Pennsylvania was slightly less in 1939 than in the previous year, but owing to higher average prices 1939 was undoubtedly a better business year. The last quarter showed markedly increased activities throughout all of the Pennsylvania fields. Production, Stocks and Price Storage of Pennsylvania crude oil at pipe lines and refineries totaled 5,413,000 bbl. on Dec. 31, 1938, and declined during the year 1,124,000 bbl. to a total of 4,319,000 bbl. at the end of 1939. The stocks of crude at the end of the year represent the lowest point reached in Pennsylvania-grade crude storage in recent years. Stocks increased slightly during April, May and June, but decreased during all other months of 1939. The Bradford field production within the state of Pennsylvania averaged 35,340 bbl. per day throughout 1939, which represents a decrease of 1419 bbl. a day from the 1938 average. The production in central and southern Pennsylvania increased 1176 bbl. per day, averaging 12,159 bbl. throughout 1939. Table 1 includes annual production for the part of Bradford field situated within the state of Pennsylvania, for central and southern Pennsylvania, and for the entire state of Pennsylvania. A definite segregation of production between the Bradford field and central and southern Pennsylvania is slightly ambiguous because a portion of the oil from the newly discovered Music Mountain pool is included statistically in each area. In all probability the entire increase and some small addition to the production from southern Pennsylvania can be attributed to oil produced from the Music Mountain pool. Within the Bradford field, six price changes occurred throughout the year. At the beginning of 1939 the price of Bradford crude oil was $1.80 per barrel, whereas by the end of the year it had risen to $2.50. The weighted average price for Bradford crude during 1939 was $2.059 per barrel.

Jan 1, 1940

By Alexander L. Field

In the light of the experimental data on equilibrium for the reaction C + FeO = Fe + CO in molten steel recently obtained by Kinzel and Egan,l it is necessary to revise current theories regarding the nature of equilibrium between carbon and FeO in the basic open-hearth furnace. According to the measurements of these investigators the equilibrium constant m for the above reaction for a pressure of dissolved CO equal to 1 atm. is equal to 0.0005 at 1550" C., when concentrations of carbon and FeO are expressed in percentages by weight. Their work also shows that, with the pressure of CO fixed at 1 atm., not only is the product of carbon and FeO constant, but carbon and FeO are each independently constant—a circumstance which might have been predicted from theoretical considerations. At 1550" C., carbon is constant at about 0.025 per cent. and FeO at about 0.020 per cent., with the pressure of dissolved CO equal to 1 atm., the product of these two constants being equal to the originally mentioned constant of 0.0005. Available data on the dissolved FeO content of samples taken from the metal bath at practical slag-metal equilibrium prove that this FeO content is determined solely by temperature and the effective FeO content of the slag. The distribution constant r at 1550" C., as determined by Herty, Gaines, Larsen, Simkins, Geruso and Watkins2 is equal to 0.0086. A slag would have to contain 0.020 = 2.3 per cent. effective 0.0086 FeO or less in order to prevent the metal from containing more dissolved FeO than that required for equilibrium with CO at 1 atm. pressure. Such low percentages of FeO are never found in basic open-hearth slags at the completion of a heat when rate of carbon drop has become practi-

Jan 1, 1930

By L. H Levenson, Charles S. Barrett

The orientation of metal crystals and grains, both large and small, can be detcrmined conveniently and accurately without the use of X-ray apparatus. This seems to be appreciated by so few metallurgists that it may be useful to explain in detail the method we have found most satisfactory in the laboratory—the reflection of light from crystallographie etch pits. This note includes a description of a suitable inexpensive instrument and instructions for etching various metals and for plotting the data. As the stereographie projection is used to facilitate handling the data, this note may he considered as an appendix to an earlier review of the metallurgical uses of the stercographie projection.&apos; Various methods involving etch pits have been used by other investigators. Bridgman&apos;s method2 consists of attaching the specimen to a sphere (a transparent sphere is convenient4 , holding it at arm&apos;s length, and marking a spot on it when it has been turned so that the eteh pits reflect light into the eye of the observer from a lamp standing behind him. It has an accuracy of about 2" and is extrernely rapid. A greater accuracy can be obtained by having the reflected light fall on a screen, as has been done by Czochralski,5 Chalmers,6 and Schubnikov.7 All of these methods have been intended for undeformed single crystals. Tammann and his coworkers3,8 developed a method for estimating the number of grains in a polyerystalline aggregate having orientations in a given region of the stereographic triangle and thus obtained statistical information about deformation and reerystallization textures. While the method has had some use in recent years,9 it is not applicable to the majority of problems in physical metallurgy. Smith and Mehl10 determined orientations by plotting the directions of the sides of individual etch pits on a stereographic projection. The accuracy is limited to about 3" and the method requires careful polishing and high magnification.

Jan 1, 1940

By Charles S. Barrett, L. H. Levenson

The orientation of metal crystals and grains, both large and small, can be detcrmined conveniently and accurately without the use of X-ray apparatus. This seems to be appreciated by so few metallurgists that it may be useful to explain in detail the method we have found most satisfactory in the laboratory—the reflection of light from crystallographie etch pits. This note includes a description of a suitable inexpensive instrument and instructions for etching various metals and for plotting the data. As the stereographie projection is used to facilitate handling the data, this note may he considered as an appendix to an earlier review of the metallurgical uses of the stercographie projection.&apos; Various methods involving etch pits have been used by other investigators. Bridgman&apos;s method2 consists of attaching the specimen to a sphere (a transparent sphere is convenient4 , holding it at arm&apos;s length, and marking a spot on it when it has been turned so that the eteh pits reflect light into the eye of the observer from a lamp standing behind him. It has an accuracy of about 2" and is extrernely rapid. A greater accuracy can be obtained by having the reflected light fall on a screen, as has been done by Czochralski,5 Chalmers,6 and Schubnikov.7 All of these methods have been intended for undeformed single crystals. Tammann and his coworkers3,8 developed a method for estimating the number of grains in a polyerystalline aggregate having orientations in a given region of the stereographic triangle and thus obtained statistical information about deformation and reerystallization textures. While the method has had some use in recent years,9 it is not applicable to the majority of problems in physical metallurgy. Smith and Mehl10 determined orientations by plotting the directions of the sides of individual etch pits on a stereographic projection. The accuracy is limited to about 3" and the method requires careful polishing and high magnification.

Jan 1, 1940