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By Samuel S. M. Chan

The magnetic susceptibilities of some ores and the major rock formations of the Precambrian Belt Supergroup in the Coeur d'Alene mining district were determined both in the laboratory by the use of the Gouy method and in the field with a Bison susceptibility unit. Trace element analysis of the same group of rock samples was also made using the atomic adsorption technique. Results of this preliminary study indicate that some correlation exists between the magnetic susceptibilities and the various rock formations. This may be useful for regional mapping and mineral exploration.

Jan 1, 1974

By Douglas W. Fuerstenau, Kalanadh V. S. Sastry

Based on an analysis of green pellet size distributions and kinetic data on ball growth with taconite concentrates, a ballability index has been developed to quantify ball growth behavior as a function of moisture and bentonite additions. The applicability of the ballability index to such other particulate materials as pulverized limestone and ground magnesite is shown.

Jan 1, 1973

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.' This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,' a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

There were two official representatives of Foreign Governments as guests at the Chicago Meeting. One was Frederick Goransson, managing director of the Saudvikens Steel Works, who represented the Jernkonteret, the Iron and Steel In-stitute of Sweden, and who came to this country especially for our meeting. The other distinguished guest was Commander Toublet, who repre-sented the French Embassy. Commander Toublet delivered a most polished address at the Banquet, dealing with the felicitous relations existing between this country and France for the last 150 years. Com-mander Toublet was accompanied by Mrs. Toublet, who won the hearts of all the ladies present, whose guest she was.

Jan 11, 1919

By Donald M. Liddell, G. C. RIDDELL

THE cosmic ray continues to engage the attention of the physicists, and according to Millikan and Compton, experiments of the past summer indicate that these rays must come from interstellar space, but not from the stars themselves. According to press reports of the International Congress of Physicists at Rome, the view was given there that these rays have an initiating potential of over 750,000.000 volts. In the field of spectrographic investigation great strides have been made. The U. S. Naval Research Laboratories (R. F. Mehl and G. E. Doan of Lehigh) have just finished a year's work with a "radium torch" or "shadowgraphic apparatus" in the field of the X-ray, that bids fair to displace the latter to a great extent. The torch is more powerful., easier to operate and cheaper. Penetration of 10 in. of steel has been accomplished, which. is much -beyond the- -scope-, of the X-ray..

Jan 1, 1932

By Elliot Rexford

The quality of aggregate materials is of major importance in governing durability and permanence of concrete structures. The problem of selecting suitable aggregate materials is two-fold. Geological factors include the type and character of the aggregate source, presence of known or suspected reactive constituents, and presence of thermally incompatible materials. Laboratory investigations include petrographic studies, soundness and reactivity tests, and tests of thermal properties. The importance of each factor in the selection of satisfactory aggregate material is considered in detail.

Jan 3, 1950

By Paul J. Fopiano

SOME relationships between the flow characteristics of iron single crystals of 99.9 pct purity and the behavior of imperfections have been investigated. X-ray rocking-curve measurements and etch-pit counts were made as a function of plastic strain, and compared to the stress-strain curve obtained on a modified Polyani tensile machine. Crystals grown from rolled strips of vacuum-melted iron by the strain-anneal method1 had a high preference for a (110) longitudinal direction and a (211) face normal. The tensile specimens were prepared from 2 by i by 0.040 in. single crystals having a gage area of 3 by \ in. Rocking-curve measurements were carried out with a highly perfect germanium monochromating crystal in which the dazz spacing was matched to that of the dZl1 in the ir0n.l Well-collimated CuKal radiation was used throughout. These procedures practically eliminated errors due to geometrical and wavelength resolution. Inasmuch as the rocking-curve half breadth may vary markedly from point to point in the specimen being irradiated, the crystals were strained in place by mounting a hydraulic loading device on the double-crystal spectrometer. The rocking curves were taken after each increment of strain in the unloaded condition, since no observable difference was found in the rocking-curves between the loaded and unloaded states. The rocking-curve half breadths of the as-grown specimens were in the range 90 to 120 sec of arc when the beam irradiated an area of about -£ by -& in. on the specimen. DeMarco and weiss3 have shown that, for a well-colli- mated X-ray beam, irradiating about 10"! sq in. of the very same material, half breadths within 10 pct of the Darwin natural half breadth were observed. Since the rocking-curve specimens were stressed by the load-unload technique, the strain achieved at any given stress depended on the time of holding because of low-temperature creep. Fig. 1 shows the rocking-curve half breadth (also area/peak height) as a function of plastic strain for a relatively short holding time (2 to 5 min) at each stress level. For strains less than 0.1 pct the rocking-curve breadth is essentially constant; it is only for larger strains that there occurs a significant increase in this breadth. Where the holding times at each stress level were longer (by well over an order of magnitude) there occurs a significant increase in the rocking-curve breadth only after plastic strains of the order of 0.6 pct had been introduced into the specimen. This observation is related to the time dependence of creep phenomena and emphasizes the difficulty in comparing data obtained by two such different straining methods. Etch-pit results were obtained using a 2 pct nital etch on specimens strained in the range of 0 to 1 pct. Prior to etching, all specimens were annealed for 3 hr at 150°C, the carbon content being sufficient to decorate the dislocations for strains of at least 1 p~t.~ The data points were all taken from parts of the same single crystal which had been strained with short holding times at stress in increments of strain of the order of tenths of 1 pct. The (211) plane is particularly difficult to etch-pit in vacuum-melted iron and therefore it is felt that these values are as much as an order of magnitude low. Fig. 2 shows the etch-pit density as a function of plastic strain. The smooth curve passing through the data points is not meant to infer a quantitative correlation with the rocking-curve data. What is of interest, however, is the change in etch-pit density in the region of 0.2 pct plastic strain. The first three increments in strain (points 2,3, and 4) did not produce a measurable change in the etch-pit density while subsequent increments did produce a measurable change. While the absolute values of these results do not appear to be cor-

Jan 1, 1967

By Culver, Richard S.

In spite of the widespread interest in rock bolt research, relatively little is known about the critical region surrounding the bolt anchor. In analyzing the stress distribution around an opening resulting from rock bolt support, it is commonly assumed that the bolt is fixed at a point far enough from the surface so that the anchor does not influence the performance of the bolt. Furthermore, a bolt anchor is assumed to per- form satisfactorily if it will hold the design load with a minimum amount of load relaxation, commonly called bleedoff. From the standpoint of the design engineer both of these assumptions are reasonable, but they ignore the fact that the extremely high stresses in the region of the anchor are capable of generating fractures in the rock. Lang estimated the bearing stresses for a slot and wedge anchor on a one-inch-diameter bolt to be as high as 125,000 psi. This paper describes a more thorough analysis of the magnitude of the stresses around the anchor and the nature of the potential fractures that might result.

Jan 1, 1968

ZAY JEFFRIES,* Cleveland, Ohio (written discussion?).-The microscope has, indeed, proved a mighty tool in the study of the structures of substances. It is limited in its resolving power to the wave length of the light used for illumination. A little in resolving power can be gained by using ultraviolet rays, which can only be detected by the photographic plate. Even the highest powered microscope only permits the study of aggregates of millions of atoms. The x-ray spectrometer, on the other hand, makes it possible to study the positions of the atoms in a crystal. The positions of the atoms in over fifty crystals have now been ascertained. But in amorphous substances the x-ray spectrometer is only able to tell us that the atoms seem to have no regular arrangement; the actual arrangement and method of grouping is still a mystery. In most perfectly formed crystals and in so-called "grains" in metals, the x-ray spectrometer teaches us that colloids seem to play no role inasmuch as the atoms are arranged in regular layers rather than in random clusters. In the boundary region between crystalline grains of like as well as unlike substances and in amorphous substances like glass, it seems probable that the random clusters, or colloids, play an important role. There still remains the application of wave lengths connecting the ultraviolet and x-rays both by direct reflection or diffraction and by the ultramicroscope. In the study of substances like glass, for example, it may be possible to identify the clusters or molecules by one wave length and to study the positions of the atoms in a cluster by using a smaller wave length. Any light that can be thrown on this important unknown subject and its relation to the properties of substances is therefore very welcome, and Mr. Alexander's paper is so written as to stimulate thought and experimentation in this direction. JEROME ALEXANDER (author's reply to discussion ?).-Col. Bancroft states' that in the case of alloys, the mass is always crystalline. While this generally may be so in the case of alloys, as ordinarily met with, before the alloy reaches this state or condition, its constituent particles must be in a still more finely dispersed state. In alloys, the speed' of transition between the finely dispersed state where the phases are amorphous, and the crystalline state where the phases are of known composi-

Jan 5, 1919

By Arthur B. Cummins, Henry Mulryan

DIATOMITE is a hydrous or opaline form of silica, commonly known as diatomaceous earth, diatomaceous silica or kieselguhr. The term "infusorial earth" has lost its original meaning and today is incorrect in view of the distinctions between diatoms and infusoria. Various locality and variety names are obsolete but some retain local significance. Moler and Celite are trade names that have become associated with diatomite products from certain deposits in Denmark and near Lompoc, California. COMPOSITION Diatomite is essentially silica with some combined water (2 to 10 pct). Frequently it contains organic matter (from traces up to over 30 pct) and varying amounts of inorganic impurities such as sand, cryptocrystalline silica, clay, volcanic ash, calcium carbonate, magnesia and soluble salts. In the natural or crude state, diatomite contains from 10 to 65 pct or more of free water. Table I gives analyses of several diatomites from deposits of different types. PROPERTIES Pure varieties, either massive or stratified, are friable and porous, of low apparent density, and somewhat chalklike in appearance. Varieties containing organic matter vary from sedimentary oozes to peatlike materials. Impure varieties may be more or less claylike, sandy, calcareous or cherty. Compacted types approach porcellanite and silicified shales. COLOR-white, cream, gray, tan, brown, greenish to nearly black. HARDNES-light-weight varieties appear 1 to 1.5 because of porosity, but microscopic particles are 4.5 to 6.5. SPECIFIC GRAVITY-1.9 to 2.35. APPARENT DENSITY---dry block form, 20 to 40 lb per cu ft; dry powder, 5 to 16 lb per cu ft. CRYSTAL SYSTEM-generally amorphous (isotropic by X-ray diffraction) but frequently showing faint cristobalite pattern.67.68,70 MELTING POINT-1400° to 1650°C. STREAK-white. LUSTER

Jan 1, 1949

Willet G. Miller, Toronto, Canada (communication to the Secretary): In his interesting paper Mr. Lindgren says: " As to ultimate results, it would seem as if we should be justified in concluding, with Prof. Suess, that the gold-supply of the world will gradually decrease if no further important improvements are made in the processes for the extraction of this metal; but regarding events so far distant no predictions may safely be made." It seems to the writer that no very important improvements require to be made in order at least to keep up the present production for many years to come. In many parts of the world there are large deposits of auriferous material which can be worked if present conditions are slightly changed. In the territory occupied by the Archean protaxis of the Province of

Jan 1, 1903

By E. W. Murbach

The oxidation of uranium carbide by oxygen at various pressures, and by air, has been investigated at temperatures up to 600°C. Arc-melted and cast uranium carbide displays oxidation behavior that appears to be dependent on its treatment after melting. ccReactive" uranium carbide, which results from exposure of freshly melted material to laboratory air, ignites in oxygen at about 275° to 350°C depending on pressure, and in air at about 350°C. The product of the initial oxidation appears to be UO2+.. Continued heating produces U30,. The initial oxidation rate is poportional, roughly, to the square root of the oxygen pressure. The activation energy determined for the initial oxidation reaction is 7.1 kcal, from 400° to 600°C in 10 mm of oxygen. AN investigation of low-decontamination methods for reprocessing uranium carbide reactor fuels is being carried out at Atomics International. One of the reprocessing cycles includes oxidation of the fuel at relatively low temperature (300° to 500°C) and reaction of the product oxide with carbon at elevated temperatures (above 1500°C) to produce uranium carbide. A number of small-scale experiments have been carried out in which uranium carbide was oxidized in air and oxygen at various pressures to measure reaction rates and to obtain other information concerning the oxidation process. In initial experiments with arc-melted UC, ignition was observed at about 275°C in oxygen or 350°C in air. However, similar experiments by Neymark' at 426°C in air showed no ignition. It was soon determined that the difference in oxidation behavior was due to the treatment of the UC following arc-melting. Neymark's experiments were carried out with freshly melted UC while those reported in the

Jan 1, 1963

By D. C. Shelton

This paper discusses the metallurgical testing procedures and their applications at the laboratories and mills of Pima Mining Co. The author shows, using discussions and case histories, that routine sampling and evaluation of daily and monthly data can be as valuable as thorough laboratory investigations and mill test work. A great deal of valuable information can be made available this way. This paper discusses laboratory and mill metal-lurgical testing procedures and their applications at Pima Mining Co., located about 25 miles southwest of Tuscon, Ariz. The Company, incorporated in 1951 (the year the orebody was found) in California to operate the Pima mine, is jointly owned by Cyprus Mines Corp., Utah Contruction and Mining Co., and Union Oil Co. Milling started in December 1956. The main Pima orebody is a contact metamorphic vein of copper-bearing hornfels with an average dip of 45° to the south with an east-west strike. The hanging and footwalls are quartzitic pyroclastics (arkosite) containing some sulfides. Barren igneous intrusions are also present. Conglomerates and alluvial wash cover the deposit to a depth averaging about 200 ft. The principal copper mineral is chal-copyrite. Native copper, chalcocite, and minor amounts of chrysocolla and other copper minerals are also present, together with sphalerite and some molybdenite. Generally, it has been noted that the ratio of chalcocite to chalcopyrite is higher in the lower grade ores, while as the grade increases, there are only minor amounts of chalcocite. Open pit mining is employed at Pima, using both trucks and an inclined skiphoist system. A detailed description of Pima Mining Co. operations was presented by Spaulding et all. More recently another orebody to the north and east of the present pit has been discovered and will be placed in operation within a few years. This ore is of a porphyritic rather than a lode nature since values are disseminated in both igneous and metamor- phosed sedimentary rocks. The new orebody is expected to be harder and cleaner than the present deposit. The views expressed in this article are those of the author and do not necessarily reflect those of Pima Mining Co. nor of the profession in general. PlMA MILL The following outline of milling practice is presented to furnish a background for later chapters of this report wherein specific problems will be detailed and analyzed. Run of mine ore is crushed in three stages, using conventional equipment to 85% minus 1/2-in. for feed to two 10 x l6-ft rod mills operating in open circuit. Each rod mill discharge is split between two 10% x 13-ft ball mills in closed circuit with three 20-in. cyclones. In addition, a 7 x 12-ft ball mill with one 20-in. cyclone receives part of the discharge from one of the rod mills. This equipment was manufactured by Allis Chalmers and Equipment Engineers. The cyclone overflows are combined, sampled and, after joining the regrind cyclone overflow, are distributed into 12 10-cell Fagergren 66-in. flotation machines. The primary rougher concentrate produced

Jan 1, 1965

By M. E. de Morton

Recovery and early recrystallization of heavily deformed, 99.98 pct Cr was investigated by studying metallographic structure. X-ray line sharpening, electrical resistivity, plastic properties, internal friction, and shear modulus. Appreciable recovery of resistivity, internal friction, and shear modulus together with some hardening and relief of internal strains occurred before the visible growth of a textured substructure above 350°C (recrystallization in situ). The complex behavior of shear modulus, internal friction, and its strain amplitude dependence during annealing are discussed qualitatively in terms of the relative mobility of dislocations. BY plastically deforming fully recrystallized 99.98 pct Cr above the brittle to ductile transition temperature, at -350°C. as in wire drawing, chromium can be made very ductile at room temperature. However, this ductility is lost on annealing at high temperatures when recrystallization takes place.' The present investigation was made to determine the general pattern of the changes in a number of physical and mechanical properties during recovery and recrystallization of heavily deformed chromium as part of an effort to elucidate the reasons for lack of ductility in the fully recrystallized condition. PREPARATION OF MATERIAL Wire specimens 0.027 in. in diam were prepared from arc-melted, electrolytic chromium by extruding, hot swaging and finally wire drawing at 300" to 350°C, i.e. above the brittle-to-ductile transition temperature. The total reduction in area of the wire was 98 pct and the last 3 pct of reduction was made at 100" to 150°C before cooling to room temperature. The impurity content of the material is shown in Table I. Internal friction and modulus measurements were made on a single specimen after annealing in situ at successively higher temperatures. For all other measurements, a fresh specimen was used for each temperature and annealing of these specimens was done in evacuated (0.001 mm Hg) and sealed silica tubes for 1 hr at the various temperatures up to 700°C. EXPERIMENTAL METHODS AND RESULTS The occurrence of a. transition in some physical properties of chromium at - 40°C2 imposed limitations on the temperature region where some of the measurements could be made. The reason for this transition in chromium is at present unknown but is probably associated with an antiferromagnetic state observed below - 40°C.* Heavy deformation produces an anomalous decrease in resistivity when measured at temperatures below -40°C4 though a normal increase is observed above this temperature. On the other hand internal friction in heavily deformed chromium5 over the temperature range 40" to 50°C is invariant with temperature. Above and below this range internal friction is strongly temperature dependent, increasing with increasing temperature. A temperature in this range was therefore convenient for both resistivity and internal friction measurements and for consistency the measurements of the mechanical properties were also made at about this temperature. No structural change has, however, been observed in careful X-ray measurements6 between -195" and 50°C, i.e. departure from cubic symmetry was not greater than 3:10,000; X-ray line sharpening measurements were therefore more conveniently made at room temperature.

Jan 1, 1962

By Nicholas J. Grant, David S. Bloom

An investigation of the Cr-Ni system has revealed that there exists a eutectoid transformation at about 1180°C. 'The transformation in chromium implied by the eutectoid reaction was detected at about 100°C below its melting point. Associated with the eutectoid transformation, a metastable transition structure has been found. THE Cr-Ni phase diagram is shown in current literature to be a simple eutectic system in which the high chromium end of the diagram is incompletely determined, Fig. 1. The last investigation of this system was undertaken in 1936.' Because of limitations in metal purity, especially of chromium, and temperature measuring techniques, the diagram should be accepted with some reservations, as was indicated by Hansen.V or examwle.-, the wresence of the compound Cr²Ni, with a tetragonal structure," remains unverified and incompatible with the simple eutectic diagram. The work reported here began because of discrepancies that appeared in experimental studies in the binary alloys Cr-Ni and in the ternary system Cr-Mo-Ni. The existing binary Cr-Ni diagram failed to provide a complete explanation of observations made by microscope, X-ray, and thermal analyses. Experimental Methods The materials employed were of a higher degree of purity than were available to previous investigators. The Mond nickel used had a nominal purity of 99.87 pct, while the electrolytic chromium analyzed 99.03 pct with the major impurity being 0.5 to 0.7 pct oxygen with some iron. All alloys were melted in a vacuum furnace to remove dissolved gases, sufficient carbon was added to the charge to combine with all the oxygen as CO. Final analysis determined the carbon as about 0.02 pct and the oxygen around 0.06 pct or slightly more. Stabilized zirconia crucibles and thermocouple protection tips were used throughout and contributed no detectable impurity to the melts, as long as the oxygen in the chromium was kept low. Heats averaged about 250 g, which permitted about 2 in. of the thermocouple protection tips to be submerged. The temperature drop across the thermocouple protection tip was determined to be about 3°C, a minor source of error. The alloys, after removal from the vacuum furnace, were placed in a furnace operating in a purified argon atmosphere for the thermal analyses. An- nealed wolfram-molybdenum thermocouples provided the primary means of temperature determination, though a Pt-Pt-10 pct Rh couple was employed for a check when possible. A sensitive, high-speed Leeds and Northrup Speedomax recording potentiometer indicated the thermocouple output. X-ray diffraction patterns were obtained primarily on a Norelco unit, which permitted diffraction angles only up to 45" (28 = 90"). In general, either rotated or stationary solid samples were used, because it later evolved that many samples were susceptible to transformation resulting from the cold working involved in pulverizing. It was also noted that rotating a sample sometimes suppressed weak lines, so, usually, samples were not rotated. Later a high temperature camera was adapted for use at temperatures up to 1400 °C on the Norelco unit utilizing both solid and powdered samples. Unless otherwise noted, all X-ray patterns were made with a chromium tube and a vanadium filter. Further-

Jan 1, 1952

By James A. Barr

Phosphate rock is a natural rock containing one or more phosphate minerals usually calcium phosphate, of sufficient purity and quantity to permit its use, either directly or after beneficiation in the manufacture of commercial products.1 The principal minerals in phosphate rock have the apatite structure which may be represented by the type formula: Ca10(X2) (PO4)6 where X represents the hydroxyl group (OH), chlorine or fluorine, either singly or collectively. The calcium may be partly replaced by sodium, magnesium, and other positive ions such as manganese, strontium, lead, uranium, cerium, yttrium and other rare earths. The PO4 radical may be partly replaced by small quantities of UO4, AsO4, SiO4, CO3, SO4, or Vo4. A typical commercial rock is usually a calcium phosphate containing 3 to 4 pct fluorine, the major impurities being limonite or other iron oxides, clay, aluminum phosphates and silica as quartz sand. A little vanadium is present in most of the domestic rock deposits (except the Tennessee Brown Rock), according to Jacob, Hill, Marshall and Reynolds! A little uranium occurs in the Florida leached zone, as will be brought out later. The chemical analyses are reported as P205, or tricalcium phosphate Ca3(PO4)2, the latter often designated by the trade name BPL (bone phosphate of lime). Commercial analyses usually report iron and alumina as oxides, lime as CaO and silica or insoluble. Colony3 examined many samples of apatite, staffelite, dahlite and American phosphorites and concluded that all have identical X-ray diffraction patterns. The phosphates in the phosphate rock have very minute crystalline structures. The mineral apatite Ca3(F.Cl) (PO4) 3 is the principal primary source of the element phosphorus, and occurs widely distributed in igneous rocks but rarely in a minable mass. Only about 12 pct of the world production of phosphate rock comes from primary apatites; the remainder is derived from secondary phosphorites. These phosphorites have been formed by the alteration of sediments by solutions containing phosphoric acid. Such solutions have come from the weathering or leaching of igneous rock containing apatite, bone deposits of prehistoric animals, marine life or guano deposits. These phosphorites are mostly alterations of phosphatic limestones. The sedimentary phosphate deposits are of marine origin and may have been enriched by subsequent solution of the more soluble calcium carbonate by waters containing carbon dioxide, by physical concentration by wave action, and by redeposition of the dissolved phosphate ions. Uses of Phosphate Phosphorus is the spark of life and is the structure builder and one of the main elements of plant food (fertilizer). Without phosphorus, life cannot exist. A "complete" plant food[t] in addition to phosphorus compounds contains potash, which acts as a catalyst to convert nutrients to useful forms, nitrogen to supply the growth element and many minor elements. The cycle of supply of phosphorus is from the apatite to solution and soil, absorption of plant life, decay and return to the soil or by animal life feeding on the plants. With insufficient supply of phosphorus in vegetation, life is not prolific. If crops are removed from

Jan 1, 1960

By R. Taggart, R. H. Ericksen, D. H. Polonis

Transmission electron microscopy techniques hare been used to study the spontaneous marfensite phase that forms during the thinning of Ti-Cr alloys. The structure of this phase has been found to differ. from the hcp martensite and has been identified as a clisforted fcc lattice. The spordaneous marlensile in this system is interpreted as a metastable isomorph of the equilibriunz TiCr, phase. WHEN thin-foil specimens for transmission electron microscopy were prepared from metastable alloys of the Ti-Cr system, a spontaneous transformation occurred' when the foils contained the untrans-formed 0 phase or two-phase mixtures of the 0 and w phases. The purpose of this paper is to examine the relationship that exists between the crystal structure of the spontaneous product and that of the matrix. The differences between the martensite transformation that occurs in the bulk material and the spontaneous reaction that occurs during the preparation of thin foils are compared with the observations that have been reported for similar phenomena in a commercial titanium alloy.' A spontaneous reaction that exhibits characteristics similar to a martensite transformation has been reported to occur in thin foils prepared from the retained metastable structures of several alloy systems.1'3"7 ~ull~ observed such a spontaneous reaction in 0 brass and attributed the apparent increase in the martensite transformation temperature to a decrease in the non-chemical free energy associated with bulk strain energy. He also showed that the spontaneous product did not have a specific habit plane, but that its orientation relationships to the parent matrix were dependen on the thickness of the transforming region. It has also been pointed out by Breedis6 that in thin films the absence of the constraints imposed by a bulk matrix can cause different requirements for the martensite plate interface and lattice distortion which is reflected bv a dependence of the transformation mechanism on the specimen geometry. In the case of the spontaneous reaction reported for Au-Zn alloys7 a definite habit plane was determined and shown to correspond with the habit plane calculated on the basis of the Bowles and Mackenzie crystallographic theory of the martensite transformation.'- lo EXPERIMENTAL PROCEDURE A series of titanium alloys containing 5.5, 5.9, 6.4: 7.6, 8.0, 11.3, and 18.7 at. pct Cr were prepared from high-purity (iochrome) chromium and iodide-grade titanium by levitation melting. The experimental procedure used for sectioning the alloys and for thin-foil preparation has been reported in an earlier paper.' X-ray diffraction patterns were obtained using a 114-mm Debye-Scherrer camera and Cu-Ka radiation. In order to minimize fluorescent radiation from the specimen, a strip of aluminum foil 0.002 in. thick was placed in contact with the X-ray film. After a specimen was removed from the camera: an additional X-ray experiment was performed, to insure that no spurious lines were obtained due to the presence of the aluminum foil. The interstitial impurity analysis for the alloys used in this study was as follows: oxygen, 100 ppm: hydrogen, 30 ppm: nitrogen, 28 ppm. EXPERIMENTAL RESULTS Electron diffraction patterns were obtained from several individual crystals of the spontaneous marten-

Jan 1, 1970

By H. O. Jahns, R. A. Greenkorn, R. E. Haring, L. K. Shallenbarger

This paper is a study of the effects of heterogeneity on flow in an analog of porous media, the Hele-Shaw model. l-3 A set of experiments in heterogeneous Hele-Shaw models showed streamlines through and around heterogeneities of various sizes, shapes and levels. (A level, we define as the ratio between the transmissibility of the heterogeneity and that of the rest of the model.) The heterogeneities were restrictions or expansions of the flow stream analogous to variations in the transmissibility of porous media. The experimental data agreed well with numerical results and with an analytical solution, which we derived for a circular heterogeneity in an infinite field. This study considers the flow-stream distortion due to the shape, size and level of heterogeneities. Size and level are much more important than shape provided the heterogeneity is not long and narrow. Our analytical solution shows that a circular heterogeneity in a large field can be replaced by an equivalent circle of either zero or infinite permeability. The radius of the. equivalent circle is a simple function of size and level of the actual circle. INTRODUCTION With the availability of high-speed computers and numerical procedures to predict reservoir behavior, we are faced with an important question. How much information about the reservoir do we need to justify the cost of the computer in any given case? To answer this question, we have to know how various reservoir parameters affect flow behavior. Reservoir heterogeneity is one of these parameters. In this study, we used a simple, two-dimensional model of porous media, the hele-shaw model, to investigate the effect of heterogeneity on flow behavior. We restricted ourselves to linear, single-phase, steady-state flow in a rectangular field with a single heterogeneity at its center. The analogy between flow in Hele-Shaw models and in porous media is easily verified. Let us first consider a homogeneous Hele-Shaw model with constant plate separation h. (The Hele-Shaw model is constructed by placing two plates, usually glass, very close together and allowing liquid to flow between them. Streamlines are made visible by introducing colored fluid into the space between the plates at a number of points across the model.) We assume a cartesian coordinate system with its origin in the middle between the plates and the z axis directed perpendicular to the glass plates (Fig. 1). The fluid flow is always in a direction parallel to the glass plates and varies from a maximum value to zero in the very small distance from the middle (z = 0) to either plate (z = h/2). For slow motion of an incompressible fluid, neglecting inertia and body forces, we have the viscous flow equation: where p is the fluid pressure, p the viscosity, and v the velocity vector with components u, v and w in the x, y and z directions, respectively. In our rase. and the derivatives of 3 with respect to x and y are small as compared with the derivative in the z direction. Therefore, approximately, with Vp and v being two-dimensional vectors in the x-y plane. Two integrations with respect to z give

Jan 1, 1965

By A. H. Duane, A. E. Miller

The high-temperature allotropy of some heavy rare-earth metals and their alloying behavior with magnesium in the 0 to 50 at. pct Mg region was studied by thermal, microscopic, and X-ray methods. Examination of a hcc phase retained upon quenching alloys of different magnesium content confirmed the existence of a bcc high-temperature allotrope in pure gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. The lattice constants of the pure metals were determined from a Vegard's Law extrapolation and .found to be 4.05, 4.02, 3.98, 3.96, 3.94, 3.92, and 3.90 + 0.02 A, respectively. In all of the systems studied, the high-temperature bcc phase decomposed eutec-toidally, when slowly cooled, into a hexagonal rare earth-Mg solid solution and a simple-cubic peritec-tic AB-type compound. In 1956, Spedding et al.' observed high-temperature resistivity anomalies in the light rare-earth metals and made several unsuccessful attempts to retain the high-temperature form of these materials at room temperature by quenching the pure metals from temperatures near their melting points. High-temperature X-ray techniques were used by Spedding et a1.' in 1959, to investigate the high-temperature allotropy of the rare-earth metals. This study showed that lanthanum, cerium, praseodymium, neodymium, ytterbium, and possibly gadolinium are bcc at temperatures near their melting points. Discontinuous changes in resistivity at elevated temperatures were also observed for pure gadolinium, terbium, dysprosium, holmium, and lutetium, thus indicating the possible existence of a high-temperature crystalline transformation in these metals. However, due to experimental difficulties encountered in the high-temperature X-ray analysis of these metals, their allotropic form was not identified. Spedding et a~.~ in 1960 observed that yttrium displayed a continuous solid solubility with lanthanum at elevated temperatures, thus showing the high-temperature structure of yttrium to be the same as that of lanthanum, i.e., bcc. Similarly, the high-temperature alloying behavior of gadolinium with yttrium showed gadolinium to be bcc at elevated temperatures. The bcc nature of the high-temperature form of yttrium was again recognized in 1960 by Eash and carlson4 in their study of the alloying behavior of yttrium with thorium. Gibson and Carlson, in a similar study of the alloying behavior of yttrium with magnesium, found that by quenching Y-Mg alloys from within the 0-solid solution region, Fig. l, they were able to retain the allotropic form of yttrium. It was the present authors' intention to use this method to show the existence of a bcc high-temperature form of the heavy rare-earth metals gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. Simultaneous with the present work, Beaudry and Daane' have shown the bcc nature of the high-temperature form of scandium. EXPERIMENTAL PROCEDURES Materials. The rare-earth metals used in this study were prepared by the calcium reduction of the fluoride and were further purified by vacuum distillation. The magnesium was obtained from the New England Lime Co. and was also purified by distillation prior to its use in the preparation of the rare earth-Mg alloys. The results of chemical and spec-

Jan 1, 1964

By M. E. Nicholson

IN order to understand how alloying elements influence hardenability through their effect on the rate of pearlite nucleation, it is advantageous to use a model to describe the mechanism of pearlite nucleation. The model which currently is most widely accepted has been described, among others, by Mehl et a1.1-3 and by Hultgren.4 Pearlite nucleation involves both the nucleation of ferrite and cementite.4,5 Cementite nucleates first, followed rapidly by the formation of ferrite at the cementite-austenite interface. The conclusion that cementite is the first phase to form during the process of pearlite nucleation is based, in part, on the observation that proeutectoid cementite is continuous with pearlitic cementite and that the orientation relationship between proeutectoid ferrite and austenite is not the same as that between pearlitic: ferrite and austenite.6,7 Recently, Smith" has suggested that the dissimilarity in orientation relations, instead of indicating the pearlite nucleation sequence, may be evidence that pearlite is nucleated in a grain adjacent to the one in which it is growing. Also, Modin9 as shown that ferrite in pearlite may be continuous with proeutectoid ferrite, and he has also shown that proeutectoid cementite is not always continuous with pearlitic cementite. Thus, it appears that the conclusion that cementite always initiates the pearlite nucleation process is open to serious question. The author believes that important evidence on the question of how pearlite is nucleated exists in the rates of pearlite nucleation of different steels. The following is a review and analysis of this evidence. If the nucleation of pearlite is considered as requiring the nucleation of both cementite and ferrite, then the time to nucleate pearlite consists of the time to nucleate the first phase to form, plus the time to nucleate the second phase at the advancing interface of the first. In the absence of a visible proeutectoid constituent, the second phase must be nucleated very soon after the first. If cementite is the first phase to form, the time to nucleate pearlite will be approximately equal to the time to nucleate cementite. Since the nucleation rate of a phase precipitating from solid solution increases with the degree of supersaturation, it would be expected that the rate of pearlite nucleation should increase with increasing carbon content. Digges10 has shown that the reverse is true. He determined the quenching velocity necessary to suppress pearlite formation in plain carbon steels as a function of carbon content. His results showed that pearlite formation could be suppressed with lower quenching velocities as the carbon content of the steel increased, at least up to 1.25 pct C, the highest carbon content he studied. Thus, it would appear that in plain carbon steels, in which pearlite is formed at the nose of the C-curve, the hypothesis that cementite nucleates first does not predict the observed change in nucleation rate. The validity of the current model of pearlite nucleation may be tested also by determining whether or not it predicts the relative influence of alloying elements on the nucleation of ferrite and pearlite. This can be done best by a consideration of the changes in a TTT diagram produced by a change in alloy content. Hultgren4 suggests that the general shape of a TTT diagram, as well as what constituents will form from austenite, can be predicted from the relative nucleation rates of ferrite and cementite. This is illustrated in the schematic diagram for a hypoeutectoid low alloy or plain carbon steel shown in Fig. 1. The C-curves for ferrite nucleation and for cementite nucleation are represented by AA' and CC', respectively, and the start of ferrite formation and pearlite formation are represented by AX and BC respectively. Adopting the current theory, Hultgren suggests that between X and C pearlite forms directly from austenite, since cementite nucleates more rapidly than ferrite in this temperature range. Conversely, at temperatures above Tx, ferrite is the first to nucleate and proeutectoid ferrite is formed. As proeutectoid ferrite grows, austenite becomes enriched in carbon, so that the cementite nucleation rate is increased. As a result, pearlite nucleation above temperature Tx is accelerated, beginning along BX and not along C'X. Temperature T, represents the temperature at which the nucleation rate of ferrite equals that of cementite. By extending this type of reasoning, using the principle that the nucleation rates of ferrite and cementite increase with increasing supersaturation of austenite with respect to these phases, it should be possible to predict the influence of carbon content on the shape of the isothermal transformation diagram. For a slightly higher carbon content than that of Fig. 1, the curve A A' representing the beginning of ferrite formation should be moved to the right, whereas the curve CC' representing the beginning of cementite formation should be moved to the left. For hypoeutectoid plain carbon and low alloy steels, this prediction does not agree with existing data. Instead, as the carbon content is increased, the pearlite curve moves to the right along with the ferrite curve and always appears to join it tangen-tially. This behavior is demonstrated by the TTT-curves of a series of manganese steels" shown in Fig. 2. In this figure, TTT-curves for four alloys containing 0.20, 0.40, 0.60, and 1.20 pct C are superimposed. The curves are identified in the figure legend. The letters F, P, and C are used to indicate the start of ferrite, pearlite, and cementite formation, respectively. In these steels, it appears that the nucleation of ferrite and of pearlite are related processes. As a result of the foregoing evidence, it is proposed that the formation of pearlite be considered as follows: Either ferrite or cementite may nucleate from austenite, then grow until the remaining phase is nucleated at the interface between the growing phase and austenite. (The growth of the first phase to form is assumed to be accompanied by a composition change in the adjoining austenite.) According to this model there are two modes of nucleating pearlite: 1—where cementite initiates the succession

Jan 1, 1955