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By B. K. Larkin, H. R. Bailey

One of the most complicated and potentially one of the most promising secondary recovery methods is that of underground combustion. A number of field tests1,2,3 have been performed recently, apparently indicating that the underground combustion process is technically feasible. Relatively little has been published concerning laboratory or theoretical investigations of the underground combustion process. A few results of laboratory tube runs have been published4,5 and these data are valuable in understanding the process. The tube run data also emphasize the complexity of the thermal recovery process. Under various conditions, problems in heat transfer, multiphase fluid flow and combustion rates arise. For example, at low temperatures the combustion process proceeds so slowly that the front cannot be propagated. It is a problem in heat transfer to predict what injection rate of air is necessary to sustain combustion in a particular reservoir. Certain fluid flow aspects of underground combustion have been studied by Wilson, et a13. In the development of some of the flow equations, assumptions of adiabatic combustion were made. Vogel and Krueger1 have devised an analog model of the heat conduction process for a constant temperature cylindrical source moving radially outward in a homogeneous conducting medium. Jenkins and Ramey7, in a discussion of the Vogel and Krueger paper, present an analytical solution of a heat conduction problem related to problems considered by Vogel and Krueger. In the present paper an idealized model of the heat conduction problem is considered, which is more general than the model of Vogel and Krueger or Jenkins and Ramey. In particular, initial well heating, vertical heat losses and arbitrary frontal velocities are included. Equations for the temperature are obtained in terms of integrals. These integrals have been evaluated numerically for the case of frontal movement corresponding to a constant air injection rate and the case of constant frontal velocity. These results are presented graphically. From these graphs one may estimate conditions under which nearly adiabatic temperatures are obtained. The application of these results requires some knowledge of reservoir thermal properties, combustion rates and residual fuel content. Assuming no vertical losses it is possible to obtain explicit evaluations of these integrals in the linear con- stant velocity case and in the radial case corresponding to a constant air injection rate. PRESENTATION OF RESULTS The geometry of the radial system is illustrated in Fig. 1 where the reservoir is represented as a slab of thickness h. By making an energy balance for an infinitesimal volume, one obtains the following equation. T= x T+F(z.r).........(1) where F (z,r) =HWv1/pc (r-r1), if z h/2 = 0, if z >h/2 . In Eq. 1, V- represents the Laplacian operator and 8 is the Dirac delta function. Eq. 1 is the well-known diff-sion equation with a source term and may be applied to a linear system. For example, if the source is moving in the direction of the x axis, then the argument of the delta function is x - 1,. In deriving Eq. 1 the following approximations were made concerning the actual combustion process: (1) all heat transfer is by conduction in a homogeneous medium, (2) the formations bounding the reservoir have the same thermal properties as the reservoir, (3) the combustion fuel is consumed instantaneously as the front arrives, (4) there is a constant fuel concentration

By A. J. Teplitz, R. J. Goodwin

A new type water shut-off for use in air drilling has been developed. The method has been 99 to 100 per rent effective in several different formations of inter-ranular-type porosity. Since costs for materials, time and equipment used are relatively small, the process should extend economies of air drilling to many new areas. The treatment involves a new technique for forming a water-inroluble precipitate within the pores of a rock. Advantage it taken of the difference in mobility of a liquid and a gas in porous media to achieve the greatest volume of precipitate in a given pore. Reactants selected for the laboratory (2nd field tests were aluminum sulfate solution and gaseous ammonia. This process has been tested in both intergranular and fractured-type porosities. It has consistently shut-of between 99 and 100 per cent of the water flowing from formations having intergranular-type porosity and perrlreuhilities ranging from a few millidarcise to over a darcy The treatment is not particularly suitable for shutting-off water from fractured formations although plugging of the order of 50 per cent or greater has been achieved in all such applications. Among advantages of the treatment are: (I) no reaction waiting rime after a relatively short placement time, (2) a low mate-rials cost of about $3/f1 of hole treated, (3) use of common service-type equipment for treatment, and (4) no unusual requirements for mixing and placement. INTRODUCTION In rotary drilling with air or gas it has been possible to increase bit life by tenfold and more than double rate of penetration over corresponding performance when drilling with mud. These factors have amounted to as much as 22 per cent savings on total cost of drilling a well. However, these advantages are rapidly lost when water is encountered in an air- or gas-drilled well because water interferes with the removal of cuttings from the hole and also gives rise to other difficulties. In attempting to combat water troubles, operators have commonly resorted to such measures as mist drilling, treatment with cement or chemicals, converting to conventional mud drilling, or setting casing. In many cases these measures have either been costly or ineffective. In an effort to overcome this problem, studies were undertaken to develop an effective and economical water shut-off technique for use in formations possessing inter-granular-type porosity. Extensive laboratory experimentation finally led to a unique method for producing a water-insoluble precipitate within the pores of a sandstone. The unique part of the treatment is use of a liquid and a gas to form the precipitate, and in this case the reactants used were aluminum sulfate solution and gaseous ammonia. The reaction between these two materials is shown in the following equation. Al2 (SO1)3 - 18 H20 6NH2? saturated Water- Solution Cat 2A1(OH)3 . n H20 3(NH4)2SO • n H20 Solid Solid That is, a solid precipitate consisting of aluminum hydroxide and ammonium sulfate is formed when ammonia reacts with aqueous aluminum sulfate. The aluminum hydroxide is insoluble in water and the ammonium sulfate, though soluble, can only be removed from the formation pores by diffusion—an extremely slow process. Although the precipitate formed by the reaction is not particularly firm, great strength is not needed for a precipitate to bridge and plug intergran-ular-type porosity. A flow path in such a system is extremely tortuous and involves a great variety of pore

By R. I. Jaffee, F. C. Holden, H. R. Ogden

Ti-Mn alloys were studied in order to determine the factors affecting the mechanical properties of &stabilized titanium alloys. The principal compositional factors have been found to be solid-solution strengthening, the martensitic transformation, and instability of the P phase. Structural factors, such as grain size and shape, were found to have more influence on ductility and toughness than on strength. THE alloys of titanium with the &stabilizing elements offer the chief hope for developing useful heat treatments. Conversely, the heat-treatment response possible with the p-stabilizing elements causes difficulties such as weld embrittlement and thermal instability during service at elevated temperature. Therefore, it is of considerable technical importance to understand the factors that govern the heat-treatment responses in these alloys, so as to be able to soften the alloys if they are embrittled by an adventitious heat treatment, to render them stable in service, or to harden them while maintaining adequate ductility and toughness. The Ti-Mn system is a good example with which to demonstrate the factors that govern strength and heat-treatment response in. a P-stabilized system. The region of the a-j3 transformation, after the work of Maykuth, Ogden, and Jaffee,' is shown in Fig. 1. The a solubilities are low. This means that, in the two-phase a-p field, partition of manganese between the two phases occurs practically only to the P phase. The solid-solution effects are therefore chiefly the result of solution in the ,8 phase. The eutectoid occurs at 20 pct Mn and 550°C, and proceeds very sluggishly. It can be ignored in heat treatments in hypo-eutectoid alloys, except for long-time storage at low temperatures below the eutectoid temperature. Even here, there is some question that diffusion proceeds far enough to involve eutectoid decomposition. Three compositional factors bear on the mechanical properties and structure of titanium a-P alloys. These are: 1—solid-solution strengthening, 2—mar-tensite transformation, and 3—P instability. Combined with the purely structural factors of grain size and shape, these govern the properties of the alloys. Perhaps the most important factor is solid-solution strengthening. The facts that manganese dissolves in a titanium to a maximum of only 0.5 pct and most of the manganese partitions to the p phase dominate the structure and properties of the a-/3 alloys. Because of the overwhelming preference of manganese for the ,3 phase, the P phase is harder and the a phase is softer. The relative amounts of both phases may be modified by heat treatment in the a-P field as application of the lever rule in the two-phase field clearly shows. A critical temperature in the Ti-Mn diagram is 800°C. This is the P transus temperature of the 6.4 pct Mn alloy, which has the lowest manganese content which will form all retained-P phase on quenching to room temperature. Any quench performed from below 800°C will produce a structure consisting of only a, a plus retained P, or retained p, for alloys of the compositions used in this work. For alloys containing less than 6.4 pct Mn, any quench from above 800°C will always result in structures

Jan 1, 1955

By E. R. Buchanan, R. E. Reed-Hill, F. W. Caldwell

Poly crystalline zirconium tensile specimens containing a sizable fraction of grains unfavorably oriented for slip were deformed at 77°K to strains as high as 9 pct. The contributions of the various twinning modes to the observed strain were deter~nlned quantitatively using measured twin volume fractions and Schrnid orientation factors. The results indicate that at very small strains twinning can account for almost all of the observed strain. At higher strains slip becomes the dominant means of deformation. The most significant form of twinning was {1121}. PLASTIC deformation in polycrystalline aggregates is poorly understood even today. This is primarily because slip cannot be easily observed or studied in the interior of a metal. On the other hand, twinning can be discerned inside a specimen after deformation. Twinning studies can therefore often yield quantitative information about polycrystalline deformation not otherwise obtainable. This investigation uses the above aspect of twinning in determining the contributions of twinning to the strain during tensile deformation at a cryogenic temperature (77°K). Polycrystalline zirconium was used as the object of study. There are several reasons why this information should be of value. In contrast to many metals, both the strength and ductility of zirconium increase with a corresponding decrease in temperature. This may be related to the fact that twinning becomes more profuse and complex with decreasing temperature. Secondly, it has been discovered that certain room-temperature properties of zirconium can be greatly improved by about 1 pct prestrain at 77°K. These include an increase in tensile elongation in critical directions by over 50 pctl and a large mechanical hysteresis effect.2 Both effects are believed to be related to twins formed by prestraining: plastic twin-boundary movements accounting for the increased ductility, and anelastic twin-boundary movements for the internal friction. Thirdly, hexagonal metals which twin primarily on only the (1012) mode (such as beryllium, zinc, and magnesium), unlike zirconium, are very limited in ductility at cryogenic temperatures. Therefore, the significance of the various types of twinning in zirconium at cryogenic temperatures is of more than academic interest. Three twinning mechanism-s have beenobserved in quantity at WOK, {1012), {1121), and {1122). Each must be considered as a unique deformation mechanism because of their markedly different twinning shears and basically different angles between twinning and basal planes, as shown in Table I. It is therefore necessary to separately consider the role of each of these twins during plastic deformation at 77°K. Fortunately, each twin possesses unique morphological features which makes its identification possible on a properly prepared metallographic section. The use of the polarized microscope3 can also greatly aid in identification of the various forms of twins. EXPERIMENTAL PROCEDURE Arc-melted sponge zirconium plate, previously describedY4 was machined into 1/8 by 1 1/4 in. threaded-end, round tensile test specimens. These specimens were deformed to the desired strains in a liquid-nitrogen cryostat mounted in an Instron testing machine. The tensile axis was the transverse plate direction. This specimen direction resulted in large numbers of grains in orientations unfavorable for deformation by prism or basal slip. Deformed specimens were sectioned, mounted in epoxy cold-mount resin, ground on metallographic papers, electropolished, and anodized to provide surfaces sensitive to polarized light. Standard quantitative metallographic procedures5

Jan 1, 1965

By R. M. Asimow, J. J. Svitak

Tile crilical resoll,r,d shear stress, CRSS, for slip of slow1y cooled Ag-All single crystals was measured at 201K. Tlze importance of short-range order and Suzuki sogregalion was inrestigated by deter~rlining llze ciic.cl of quenching on the CRSS. Thr obserz.ed rfrtenching effects were generally small and indicate that short-range ordcr and Slczuki srgregation do no1 account for n significant portion of the solid-solution strengthening in this system. However, all alloys slzozcwi yield drops ulhich rilere heat- lreat nrenl-sensiline THERE have been a number of mechanisms proposed to explain alloy strengthening in the Ag-Au system. The effectiveness of some of the proposed mechanisms, especially those that depend on Suzuki segregation1" or on short-range order,2-6 SRO? should be strongly dependent on heat treatment. Since internal friction investigations in this system indicate that there is stress-induced order,' we must also consider the possibility of local atomic rearrangement or short-range ordering in the stress field of a dislocation. There is not complete agreement whether these mechanisms should be most effective in raising the flow stress, in causing yield drops. or some combination of these two effects. This work was undertaken to determine the effects in the Ag-Au system of mechanisms that depend on segregation or order by using known but drastically different cooling rates following a high-temperature treatment. By comparing the critical resolved shear stress, CRSS, for slip measured after a very slow cool and again after a fast cool (quench) of the same crystal, it is possible to determine the effect of cooling rate on CRSS* and on yield drops. The single-crystal CRSS was determined at several compositions because there has been no data published across the phase field since the publication of room-temperature flow stress by Sachs and Weerts.' EXPERIMENTAL PROCEDURE Starting with materials of 99.999 pct purity, single-crystal specimens of random orientation 1.25 mm square by 4 cm long were prepared with 0, 10, 14, 25, 30. 50, 70. 75. 80, 90. and 100 at. pct Au. Crystals were grown in an inert atmosphere using a modified Bridgman technique with a growth rate of 1.5 cm per hr in a gradient of 3°C per cm. To obtain a maximum practical degree of SRO, the crystals were cooled at a rate of 275'C per hr to about 310°C and then cooled at 6°C per hr to approximately 200°C. Specimens were tested in tension immersed in an alcohol bath at -72°C (201°K) at a strain rate > = 0.003 mm"1 to determine the CRSS (7). The activation volume of several crystals was determined from the flow stress increment (72 - T1) for a tenfold increase in strain rate. The total shear strain varied from 0.05 to 2.3 pct but was generally less than 0.4 pct. After testing, each crystal was then held at 500°C for 10 min, quenched into brine at -35°C and. after storage at -71°C for 1 day, retested in tension using a procedure identical to that of the first test. The quenching apparatus, see Fig. 1, was designed to enable accurate temperature control and rapid quenching while preventing specimen contamination and accidental deformation. Test data from a specimen with a fine thermocouple spot-welded to it indicated a cooling rate of 104C per sec. The relatively low heat-treatment temperature was chosen to minimize quenching defects caused by a large vacancy

Jan 1, 1970

By A. A. Bauer

The ?-to-? transformation has been studied in zirconium alloys containing 22 to 70 wt pct U. In this range of compositions the ? phase can be retained by quenching. Transformation to ? occurs by a nucleation-and-growth process. The diffusion of atoms to preferred lattice sites to yield a partially ordered structure apparently controls the rate of reaction. Alpha uranium and a zirconium precipitate from the supersaturated E phase initially formed in alloys outside the equilibrium E phase composition limits. ZIRCONIUM-Uranium alloys have long been of interest for reactor-fuel applications because of the low thermal-neutron cross section of zirconium. Considerable information is available on the various properties and behavior of these alloys1 although there had been a number of areas where information was incomplete. As part of a program to provide more detailed knowledge in these areas, the presently reported investigation was undertaken. The constitutional diagram of the zirconium-uranium system is shown in Fig. 1.' The system is distinguished by a region of complete solid solubility between the body-centered cubic ß-zirconium and ? uranium phases and the existence of an intermediate phase in the vicinity of 50 wt pct U. This intermediate phase, designated as E, is reported3 to have a primitive hexagonal structure with a = 5.03 and c = 3.08A. The structure is partially ordered with zirconium atoms at the 0, 0, 0 position and zirconium and uranium atoms located randomly at the 1/3, 2/3, 1/2, and 2/3, 1/3, 1/2 positions. While the E phase may be nominally designated as of UZr2 stoichio-metry, the random distribution of uranium and zirconium atoms permit a considerable range in composition. Of interest in the research performed were alloys in the range from 20 wt pct (10 at. pct) to 70 wt pct (47 at. pct) U. In this range of compositions the body-centered-cubic ? phase can be retained either completely or partially on quenching. The nature and kinetics of transformation of the ? phase were the subject of study. Proceeding concurrently with the presently reported work was an investigation by Kearns4 which has since been reported. Kearns studied alloys containing 50 to 60 wt pct U prepared from sponge zirconium. While the work reported here is for alloys prepared from crystal-bar zirconium and the techniques of study are to some extent dissimilar to those employed by Kearns, general agreement so far as results and interpretation can be reported. Experimental Techniques—Alloys were prepared and the transformation of the ? phase studied during interrupted-quench and quench-and-temper isothermal heat treatments by means of hardness measurements and X-ray diffraction and metallographic techniques. The isothermal transformation of the ? phase on quenching and tempering was investigated further employing dynamic-modulus measurements. Electrical resistivity and limited Hall coefficient measurements were also obtained as part of the study. Alloy Preparation and Heat Treatment— Alloys containing 15, 20, 22, 30, 40, 45, 50, 55, 60, and 70 wt pct U were prepared from as-reduced uranium and crystal-bar zirconium. The alloys were double arc melted by consumable-electrode are-melting techniques. The final ingots were forged and rolled at temperatures between 790" and 840oC to 1/4-in. rod and 1/8-in. sheet. Chemical analyses of the fabricated alloys were

Jan 1, 1961

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.' Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

By Robert A. Rapp, Jan E. Verfurth

From the measurement of internal-oxidation band widths in Ag-In and Cu-A1 alloys, products for the solubility No and the diffusivity Do of oxygen in silver and apparent NODo products in copper have been obtained over a range of temperature. The NODO products for silver are in agreement with the product of the individually determined No and Do values of Eichenauer and Müller. Although interstitial diffusion of oxygen in silver is expected, the temperature-independent factor Do of the diffusion coefficient does not agree well with the theory of Wert and Zener. For Cu-A1 alloys internal oxidation does not follow the expression derived for ideal kinetics, since the apparent NODo product calculated from internal-oxidation measurements is a function of the alloy content in the specimen. Thus, unequivocal values for No or DO or even the product NODO in copper are not available from the literature. RELIABLE values for the saturation solubility NO and diffusivity DO of oxygen in fcc metals are lacking and difficult to determine, partially because internal-friction measurements are not applicable. Permeability experiments and Sieverts7-type adsorption -desorption methods3 have met with difficulty; however, Eichenauer and Müller4 have recently reported on the solubility and diffusivity of oxygen in silver as determined by the latter technique . Rhines, Johnson, and Anderson,5 and independently Meijering and Druyvesteyn,' introduced the possibility of deriving values for the product NODO in a metal from measurements of the widths of internal-oxidation zones (subscales) formed during the internal oxidation of alloys. In addition to these authors, several other investigators7-9 have made such measurements in various silver and copper alloys at various temperatures, mostly using me- chanically polished specimen surfaces. The purpose of this investigation was to determine over a range of temperature the calculated products NODO in silver and copper from systematic measurements of the widths of internally oxidized zones in Ag-In and Cu-A1 alloys, using specimens with electro-etched surfaces. Consider the internal oxidation of a dilute solid-solution alloy in which the base metal is not oxidized. If diffusion of oxygen is the rate-controlling step, then the depth 5 of the internal-oxidation zone is given by where y is a dimensionless parameter and t the oxidation time. Based on the solution of the diffusion equation, wagnerl0 has shown that under certain conditions several mathematical simplifications may be used in the evaluation of y, so that Eq. [I] may be expressed for the case that y « 1, and y(Do/DB) 1, where N(so)the is the equilibrium solubility (mole fraction) of oxygen in the solvent metal for the given oxidizing atmosphere, is the mole fraction of the solute metal in the bulk alloy, 4 is the diffusivity of the solute in the base metal, and v is the ratio of oxygen atoms to solute atoms in the precipitated oxide BO,. Rearranging Eq. [2] Maak' has derived an expression analogous to Eq. [3] for the case that an external-oxide scale, in addition to an internal-oxidation zone, is formed. For this combined external and internal oxidation for the case that 5/2 where 5 is the distance of the internal-oxidation front from the original external s.urface, and X is the distance of the external oxide/metal interface from the original external interface. The function F is defined by the expression

Jan 1, 1964

By M. A. Cook

Sutherland used an ion-pair adsorption model to derive the author's hy-drolytic pee-acid) adsorption equation for the contact bubble curves of Wark and Cox. To do so it was necessary to postulate that the sum of coverages of surface anion sites by the collector and depressant anions is practically unity. It is here shown that the free energy of Sutherland's postulated collector ion (x-)-depressant ion (OH-) exchange reaction (for no other than the OH- to compete with X-), namely EX + (OH-) Z SOH- + X-, is in some cases positive and X- should not even adsorb. Also, in many cases the (OH-) adsorption must be quite negligible even though the collector covers only about a sixth of the mineral surface at the threshold of air bubble contact. This, however, contradicts the postulate that permits one to derive the correct bubble contact eqwztion for the ion-pair model. Furthermore, the requirement for charge neutrality leads in the ion-pair model to the (impossible) constancy of the ratio @+)/(OH-) along a contact bubble curve in which pH may change by more than seven units. HYDROLYTIC ADSORPTION EQUATION Hydrolytic (free-acid or free-base) and ion-pair (H', X-, or R', OH-) adsorption models of the collector in metal sulfide and similar flotation systems are superficially alike and somewhat difficult to differentiate. This is because they yield, under seemingly valid assumptions, equivalent forms of the equations describing the distribution of the collector between the aqueous solution and the mineral surface. This has been discussed by the author and associates1-4 and more recently by Sutherland,' both for simple collector-mineral and for more complicated collector-depressant-mineral systems. In the hydrolytic adsorption model the equations describing the contact bubble curves of Wark and coxeJ7 are as follows :2 Here X is the collector anion, D- the depressant anion, 9, and On are the fractions of the free-acid sites S on the surface of the mineral covered by collector and depressant free acids, respectively, and @ is the fraction of uncovered sites. Kx is the free-acid collector dissociation equilibrium con- stant, K1 that for the free-acid collector adsorption, KD that for the free-acid depressant dissociation, and K2 the equilibrium constant for the free-acid depressant adsorption. Eqs. 1 to 5 yield upon simultaneous solution the result is the critical free-acid concentration for bubble contact in the absence of depressant-free acid. Eq. 8 expresses the conditions along a simple collector-mineral contact bubble curve for the case HD = 0, or V = 0. Last and Cook showed that Eq. 6 applies generally and with good accuracy in the collector-depressant-metal sulfide mineral systems. Inci-dentally, it has been shown by infrared absorption studies that in some cases the free-acid adsorption process splits out water.' In this case, Eq. 2 might be written SHOH + HX Z SHX + H20, with a similar equation replacing Eq. 4 for depressant-free acid-water exchange. This possibility does not change, however, the basic equations or considerations of the hydrolytic adsorption model. Indeed, this type of free acid-water exchange reaction was predicted for fluorite and iron ore flotation by oleic acid in the dry grinding and boiling processes.410

Jan 1, 1961

By K. P. Gupta

The Cb-rich boundary of the (Cb,Al) a phase field at 1250OC is near 41 pct Al. The Al atoms tend to occupy the C. N. 12 sites in this structure. A homologous (Ta,Al)a phase was identified. No a phase was found in the Mo-Al system at 1200°C. The first binary o-phase with a non-transition element as a major component was found1,2 in the Cb-Al system. The composition of this phase was reported2 as approximately 34 at. pct Al, based on X-ray diffraction patterns taken of alloys in the as-cast condition. Further study of the composition of this o-phase, therefore, appeared desirable. Since Si was previously found3,4 to occupy preferentially the lowest C.N. sites (I and IV) in the a phase, and preliminary resultsa indicated that Al may show similar ordering, one of the aims of the present work was to obtain more complete information on ordering in (Cb, Al) o. Among the binary systems of Al with Ti-, V-, and Cr-group elements, the Ti-Al, Zr-Al, V-Al, and Cr-Al systems are known to comprise no o-phase. In the present work a Ta-Al and a Mo-Al alloy were studied in an effort to find additional o phases with Al as a major component. EXPERIMENTAL PROCEDURES AND RESULTS An alloy with the intended composition of Ta + 40 at. pct Al was prepared by arc melting in He atmosphere. In both the as-cast condition and after annealing for 10 days at 1250°C and quenching in cold water this alloy consisted of two phases, as seen in the X-ray pattern and the microstructure. One of these phases was identified as the o-phase; the observed and calculated d-spacings are shown in Table I. The lattice parameters of this o-phase are a = 9.972 A, c = 5.214 A and c/a =0.5228, as determined from a Debye-Scherrer pattern using Fe K a radiation. The d-spacings for the unknown second phase are given in Table 11. The alloy contained approximately 25 pct of the unknown phase after annealing, as estimated on the basis of microscopic examination. A Mo-Al alloy was prepared by arc melting, with an intended Al-content of 35 at. pct. The alloy button was annealed for 7 days at 1200°C and water quenched. The X-ray pattern of the alloy in both the as-cast and the annealed state showed the reflections of Mo3Al (Cr30 type structure) and an unknown phase different from a. Six Cb-Al alloys were prepared in the composition range 30 to 50 pct Al. All alloys were arc melted in He atmosphere. After annealing for three days at 1175oC in evacuated silica capsules and quenching in water, the alloys with 30 to 40 pct Al contained three phases, namely the o-phase, Cb3Al (Cr3O-type structure) and an unknown phase. The alloys with more than 40 pct Al contained two phases, namely, what appeared metallographically, the o-phase and the same unknown phase. In the alloys containing less that 38 pct Al, the unknown phase was not present after annealing for 4 days at 1250°c,

Jan 1, 1962

By J. L. Fitch, B. G. Hurd

The presence of gypsum in samples subjected to standard core analysis introduces serious errors in the measurement of water saturation and porosity. The magnitude of these errors, depending upon the type of analysis procedure used, has been evaluated experimentally and theoretically. Water-saturated pore volumes determined by vacuum distillation or retort procedures may be too high by as much as 48 per cent of the volume of gypsum present. The maximum error in this value determined by Dean-Stark extraction with toluene is 36 per cent of the gypsum volume. If pore space is measured by a Boyle's law type porosimeter the maximum erorr due to gypsum is 38 per cent of the original gypsum volume present. The conscientious core analyst may eliminate the errors caused by gypsum by either of two methods. He may apply suitable corrections for the water of crystallization removed from gypsum, or take special precautions to prevent dehydration of gypsum during core cleaning and alzalysis procedures. These alternatives are discussed and methods for obtaining reliable core analysis data are proposed. Gypsum (CaSO4 . 2H2O) occurs as a common mineral in many of the world's sedimentary basins. In addition to its presence as primary bedded evaporitic deposits, it is often found as secondary replacement zones and pore-fillings in host rocks. That it may cause false indications in porosity, both on neutron logs and in standard core analysis, has been generally recognized. False porosity interpretations from neutron logs result because the chemically bound water in gypsum attenuates neutrons as effectively as free water. Errors in core analysis result when gypsum is dehydrated prior to or during the analysis. Vacuum retort procedures used by many laboratories to determine fluid saturation and porosity effect a complete removal of water of crystallization from gypsum. The crystal water, distilled and collected with free water from the sample, is counted as water-sat11rated pore space. Dehydration of gypsum results in a decrease in volume occupied by calcium sulfate and a corresponding increase in pore volume. Thus, if gypsum is dehydrated by sample cleaning and drying procedures, subsequent porosity measurements with gas expansion or compression instruments will be high. The qualitative effect of gypsum on porosity determinations by retort procedures was discussed in a recent article by Bynum and Koepl3. They concluded that since false porosity was interpreted as being water saturated, determinations of oil content were not affected. Others in the industry, however, have pointed out that porosity values are often used with values of water saturation determined independently, e.g., from electric resistivity logs in making reserve estimates. Values of water saturation calculated from the formation resistivity using the Archie equation, S4= are actually low if values of are high due to gypsum. In this case, false porosity values due to gypsum could cause serious errors in calculations of oil-in-place. This investigation was made to determine quantitatively the effect of gypsum on porosity values determined by different core analysis procedures. EXPERIMENTAL PROCEDURES Dehydration of Gypsum The extent and rate of removal of water of crystallization from gypsum under conditions encountered in core analysis procedures were studied. Taken for the experiments were three types of relatively pure, naturally occurring gypsum, viz. selenite, satin spar and massive gypsum. Although all samples probably contained trace chemical impurities, each type lost the theoretical amount of water upon complete dehydration. An automatic recording thermobalance, similar to one described by Mauer2, was used to obtain dehydration rate data for samples heated in dry air. Water

By D. L. Albright, R. W. Kraft

Solidification experiments were conducted with the objective of testing the theory of eutectic colony formation. Appropriate control of variables in tests on a series of high-purity aluminum-copper specimens of eutectic composition resulted in the observation of three types of eutectic microstructures, these being a unique structure consisting of lamellae essentially parallel to one another, a banded structure, and the colony structure. Lamellar faults, which are morphologically similar in many respects to edge dislocation models in crystals, produced a complex substructure in these specimens. SOLUTE rejection at the advancing solid-liquid interface of a unidirectionally solidified single-phase metal can cause the liquid immediately in front of the interface to become constitutionally super-cooled below the equilibrium liquidus temperature. Constitutional super-cooling occurs if the solidification rate, R, is too rapid, or if the thermal gradient in the liquid at the interface, G, is too low. 1 This constitutionally supercooled layer in turn stabilizes a cellular rather than a planar interface.&apos; A similar cellular interface has been observed when lamellar and other types of eutectics were unidirectionally solidified, and it has been shown that the cellular interface led to the formation of eutectic colonies.&apos; The lamellar structure is fan-shaped at the edges of colonies (which correspond to valleys or grooves in the cellular interface) because the lamellae grow normal to the local interface. One of the possible mechanisms which might cause the formation of the cellular interface, in the case of solidifying eutectic alloys, is constitutional supercooling of the liquid with respect to a third component rejected by both phases of the eutectic.3,4 On the basis of the analogy between the solidification of single-phase metals and binary eutectics, a eutectic alloy should solidify with a planar interface if the ratio of G/R is sufficiently high to compensate for any impurity which might be present and causing constitutional supercooling. The fan-like microstruc-ture of eutectic colonies should not occur under these conditions and the lamellae should be parallel to one another and to the solidification direction for extended distances. The experiments conducted in this investigation were designed to test these ideas. Following a resume of the experimental procedure, the various microstructures observed during the study are described, and their relationship to the growth conditions which produced them is discussed. EXPERIMENTAL PROCEDURE The eutectic between an aluminum solid solution and 0 phase (approximate composition CuA12) was chosen for this work for the following reasons: it was known that a lamellar structure forms, the eutectic temperature is low enough to facilitate experimental work, and the components can be procured commercially in a very pure form. High-purity copper (est. 99.999 pct Cu, obtained from National Research Corp.) and spectrographic aluminum rods, having impurities other than copper estimated to be Zn-15 ppm, Mg-10 ppm, Fe-3 ppm, Na-2 ppm, Cd-1 ppm, and Mn < 1 ppm, were melted in a stabilized zirconia crucible in a vacuum induction furnace at a pressure of 10 pof Hg. The melt was superheated to about 1000°C to assure mixing, cooled to 780°C and cast into an investment mold which yielded sixteen cylindrical specimen blanks 1/2 in. in diam and 5 1/2 in. long. The casting was allowed to solidify under vacuum. This master heat had an analysis of 32.6 wt pct Cu and 67.4 wt pct A1 by difference. The cylindrical specimen blanks were remelted and solidified unidirectionally in an apparatus illustrated schematically in Fig. 1. An RF induction coil heated

Jan 1, 1962

By B. A. Shaw

Historically, microwave tubes have been fabricated from massive metal and ceramic components. The current trend is to lighten tibes for airborne applications. The reqciiremenls of light weight and also reduced cost have created a novel approach to tube structure in which thin-film technology plays a major role. Although the electrical requirements of thin-film circuits in microwave tubes differ from those required or se,niconductor integrated circuits. the technology is basically similar. The stringent requirements of the micvowave tube have created sophisticaled thin-film techniques thut are of interest to the integrated-circuit industry in general. This paper describes a nunzber of thin-jilm techniques recently developed and discusses in detail the application of the technology in microwave tubes. The particular areas of interest are: 1) ceramic mounted thin-film slow-wave structures; 2) thin-film secondary emitters; 3) suppression of tube environnental multipactor by semiconducting&apos; thin films; and 4) age-hardenable and dispersion-hardened thin metal films. SEVERAL thin-film techniques specifically applied to microwave power tubes are discussed in this report. There are two reasons for this work. One is the necessity of reducing weight and cost of microwave tubes and the other is related to overcoming problems in the tube operation by the use of applied thin-film technology. The major emphasis of this work has been on tube slow-wave structures. Other work in the area of secondary emission, either its suppression or its enhancement, is continuing; the most satisfactory results to date have been by utilization of thin-film technology. The requirements of high thermal and electrical conduction together with greater strength than normally obtained with elemental materials have led to the development of dispersion-hardened films. The paper will discuss: 1) ceramic-mounted delay-line microwave tubes; 2) multipactor and secondary emission; 3) hardened films. I) CERAMIC-MOUNTED THIN-FILM SLOW-WAVE STRUCTURES In a conventional crossed-field microwave tube, the slow-wave or delay-line structure is produced from two carefully machined components. One half of the structure is shown in Fig. 1. The other half is the mirror image of the first but is rotationally offset by a half a period. The combined structure now forms an interdigital type of slow-wave structure and is the anode of the tube as shown in Fig. 2. The period and finger length of an interdigital slow-wave structure are prescribed by the desired dispersion characteristics. The typical design is as shown in the first figure; it can be noticed that the finger width is several times greater than the finger thickness. Even assuming that it were mechanically possible to produce free-standing fingers of extremely small cross-sectional dimension, for example, 0.002 in. thick by 0.005 in. wide by 0.500 in. long, decreasing this finger width would increase the tube efficiency but would also decrease the thermal-conduction path, causing an increased temperature rise from intercepted rf current which in its extreme could easily cause finger melting. Hence, for free-standing lines of this type, the design is a compromise between mechanical capabilities, tube efficiency, and thermal dissipation. These structures are also expensive and tend to be heavier than purely electrical considerations would demand. In the present approach, we have transposed the three-dimensional structure previously shown into an essentially two-dimensional structure as shown in Fig. 3. The linear structure is used here for clarity of detail. The support member is a ceramic material and the line is deposited copper. The final tube design is shown in Fig. 4. Because of the backwall sup-

Jan 1, 1967

By George P. Chapman

Mica is a platy mineral occurring in a variety of complex hydrous aluminosilicate forms with differing chemical composition and physical properties. Principal minerals in the mica group include: Muscovite-potassium mica (colorless or pale green/ ruby) Phlogopite-magnesium mica (dark brown or amber) Biotite-magnesium-iron mica (black or dark green) Lepidolite-lithium mica (lilac) Selected properties are given in Table 1. Muscovite is most important commercially with phlogopite of lesser use. The laminated structure of mica enables it to be split into very thin films which are transparent and tough as well as having outstanding dielectric and insulating properties. Commercially, mica is used in a number of forms (Chowdbury, 1941; Rajgarhia, 1951; Skow, 1962). Sheet mica consists of flat sheets mined from naturally occurring books of mica, free from defects and capable of being punched or stamped into required shapes. Sheet mica is separately classified into blocks, films, or splittings according to thickness. Built-up mica, or micanite, is made by arranging overlapping splittings in layers , cemented with a binder and pressed together at high temperature. Reconstituted mica, or mica paper, is made by depositing fine flakes of high-quality scrap mica in a continuous film impregnated with binder. Scrap and flake mica are normally unsuitable in quality or size for making sheet mica. Originally the term scrap mica referred to the waste byproduct of mining and fabricating sheet mica, and distinct uses were developed for this material. Subsequently it became economically feasible to mine lower quality mica for these uses, and the term flake mica was introduced. Although the two terms are still used somewhat synonymously, it is considered better, at least in the United States, to use the term flake mica in referring to mica mined for uses other than as sheet mica; and to restrict the term scrap mica to mica mined for or with sheet mica, but which will not meet the specifications. Synthetic mica, such as fluorophlogopite, is produced by slow crystallization of a melted blend of pure raw materials. Mineralogy In the true sense the term mica does not relate to, a particular mineral, but to a group or family of minerals of similar chemical composition and to some extent similar physical properties. These minerals are predominantly potassium aluminum silicates with varying amounts of magnesium, iron, and lithium. The precise formulas and isomorphic relationships of the various group members have been studied, but general agreement has not been reached (Grimshaw, 1971; Hurlbut, 1952; Skow, 1962). The general formula describing the chemical composition of micas is [X2Y4-6Z8020(OH, F)4, where X is mainly K, Na, or Ca; Y is mainly Al, Mg, or Fe; Z is mainly Si or Al (Deer, et al., 1962).] These minerals have an internal structure of the layered lattice type where the silicon atoms are in the center of a tetrahedral grouping of oxygen atoms. The groups are linked together in a single plane by three oxygen atoms that lie within the common plane. Each of these oxygen atoms is shared by two tetrahedra. These linked tetrahedral groups, when continually extended, produce a hexagonal network within the plane. This internal structure of the mica has been used to explain the ex-

Jan 1, 1983

By F. V. Lenel, J. A. Dromsky

The influence of thermal and mechanical treatments upon the elevated-temperature stability, the microstructure, and the mechanical properties of aluminumaluminum oxide alloys is investigated. Compacts from atomized and flake aluminum powders were sintered at temperatures just below the melting point of aluminum in a vacuum of 10-4 Torr for several hours and were then hot-extruded. During this treatment the hydrated oxide present on the surface of the powder particles decomposes, the water vapor produced reacts with the aluminum forming additional oxide, and the hydrogen developed is removed by diffusion to the surface. Extrusions of compacts so treated are stable at temperatures up to the melting point of aluminum and do not form blisters and internal defects typical of extrusions from untreated powder. Electron micrographs of extrusions from unsintered compacts show long parallel oriented platelets typical of the IN previous investigations1,2 the properties and structure of aluminum alloys were described which had been produced by cold compacting aluminum powder and then hot pressing and extruding the compacts. Both the structure and the properties of these alloys differ significantly from those of commercially produced aluminum-aluminum oxide alloys. When commercial alloys are produced, they are given a sintering treatment in air at about 600°C between cold compacting and hot pressing.3 During this treatment the hydrated oxide, which forms the coating on the aluminum-powder particles from which the alloys are prepared, is decomposed.4 The chemically bound water which is released reacts with the aluminum and forms aluminum oxide and hydrogen. Most of the hydrogen is eliminated by hydrated oxide skins on the original powder particles, while the oxide particles in extrusions from sintered compacts are broken up. The strength of extrusions from treated powder is somewhat lower, but their ductility is considerably improved over that of extrusions from untreated powder. The slip-trace patterns on electron microgvaphs of extrusions which had been strained in tension before replication indicated that the grain size of the extruded alloys was approximately the same as that of the original powder particles. Coarse-grained alloys were produced by severe cold work and annealing of the extrusions. They have significantly lower room-temperature strength, but about the same ductility as the vacuum-sintered fine-grained alloys. The size and shape of oxides in the coarsegrained alloys is similar to those of the fine-grained alloys, but the particles are somewhat more uniformly distributed. diffusing to the interior or exterior surfaces of the compact, but it is difficult to eliminate all of it because the solubility of hydrogen in solid aluminum is very low even near its melting point. Extruded alloys which are not sintered before hot pressing and extrusion appear quite sound upon metallo-graphic examination, but develop severe surface blistering and internal fissuring when they are heated to elevated temperatures after extrusion. Fissures and blisters have been observed even in commercial alloys which had been sintered in air, although they are much less severe.&apos; Because of the importance of this sintering treatment it was studied in this investigation in a modified form, using vacuum sintering rather than sintering in air, to insure more complete elimination of occluded hydrogen. The technique is described and the effect of the treatment upon the structure of the alloys is documented. It has been known for some time that extruded aluminum-aluminum oxide alloys are very finegrained, but an exact delineation of grains in electron micrographs has not been possible. In the conventional metallographic-etching techniques etchants attack the interface between the second-phase particles and the matrix in the alloys much

Jan 1, 1964

By E. F. Bailey, W. J. Harris

THE temperature of the ferrite to austenite re-action is established frequently by continuous heating experiments. However, equilibrium studies of this reaction have demonstrated that austenite may form at temperatures considerably below those at which the reaction is first observed during continuous heating. Because of this discrepancy, tempering is sometimes performed above the true critical temperature and in these cases austenite forms during tempering. The lowest temperature at which austenite forms and the kinetics of the reaction have been studied by Bain,&apos; Bleakney and Gros-venor,2 and Dube and Cunningham. This austenite can affect the properties either as austenite per se, if it is retained at room temperature, or as a decomposition product if it transforms. The effect of austenite formation during tempering on low temperature impact properties of an 8 1/2 pct nickel steel was reported by Brophy and Miller4 in work published after the present investigation was initiated. They concluded that the improvement in low-temperature notch toughness which followed tempering at certain temperatures could be attributed to the austenite formed during tempering. Kramer et al.5 found anomalous hardness increases and embrittlement after tempering of a low-carbon manganese-nickel steel. They concluded that austenite formed during tempering, and that the decomposition products were responsible for the increase in hardness and the embrittlement. Quan-titative correlations of the microconstituents and mechanical properties were not made by these investigators. The present study was undertaken in order to establish the kinetics of formation of austenite at various temperatures, the characteristics of the decomposition of this austenite, and the relationship between mechanical properties and the phases present. Experimental Procedure A low-carbon manganese-nickel steel was selected because of the sluggishness of its austenite decom-position reactions. The composition of this steel in percent was: C, 0.10; Mn, 3.52; Ni, 2.34; Mo, 0.52; Cr, 0.17; Si, 0.19; V, 0.15; P, 0.019; and S, 0.020. Samples were prepared by forging sections from a large ingot to 3/4 in. bars. Formation and decomposition of austenite were investigated by dilatometric techniques which were checked by X-ray measurements. Dilatometer specimens were hollow cylinders 1 in. long, 1/2 in. diam, with a 1/8 in. central hole. All specimens were aus-tenitized for 1 hr at 1650°F and quenched in water prior to insertion in the dilatometer. Oxidation was prevented by using an inert atmosphere of purified nitrogen. Dilation was measured with a dial gauge which could be read by interpolation to 0.00005 in. Temperature was maintained within ± 3°F by a Brown Electronik Controller. Chromel-alumel thermocouple leads were welded to opposite ends of the specimen with the specimen serving as the hot junction. As a check on temperature uniformity comparison was made of the specimen temperature as measured with the chromel-alumel leads and the temperature of the center of the specimen as measured with a calibrated platinum—platinum-rhodium thermocouple embedded in asbestos in the central hole of the specimen. During heating a 5°F temperature difference was noted below 1000°F, but none above, while in cooling, a 5°F difference was observed from 1300" to 735°F, but none below. Heating rates of 35°F per min and cooling rates of 60°F per min were employed for all dilatometric studies. For transformation studies below room temperature, the dilatometer was allowed to cool to 150°F and then was quenched into liquid nitrogen.

Jan 1, 1951

By M. C. Fuerstenau, A. M. Gaudin

A homogeneous suspension is viewed by X-rays. The radiation density seen, affords a measure of the extra absorption due to the solids contained. This radiation density, at a predetermined depth, varies with time. The chart of this relationship gives the desired determination. s it is frequently necessary to know the distribu-rt tion of particle sizes in various products used in industrial applications, a number of means have been devised for these determinations. Some of them include direct microscopic measurement, screening of product, extraction of samples from a settling slurry, air and liquid elutriation, adsorption of gases and liquids, and light absorption. The absorption of light as a means for particle size analysis has been known and employed for some time. X-ray absorption has not received the attention that light has enjoyed primarily because of the complex and costly instrumentation involved with X-rays. In 1954, Brown and Skrebowskil suggested the use of X-rays for this type of determination but did not supplement their suggestion with experiment. In 1958, the authors conducted size analysis experiments on suspensions of quartz with the Trans-viewer: an X-ray unit specifically adapted for sedimentation research, and Rossa conducted experiments in a similar manner in 1959 with a stable gamma emitter, AmZ4l, on suspensions of uranium oxide. To illustrate the applicability of X-ray absorption for analyzing particle size distributions, an essentially mono-energetic and well collimated X-ray beam was used as a source. The beam was made mono-energetic by placing a zirconium filter before the counting window together with feeding the pulses from the proportional counter into a reverter, a device capable of discriminating against pulses of various heights. The sketch in Fig. 1 shows the collimation arrangement in more detail. As shown, the X-ray beam was collimated by inserting a 3/8-in. ID pipe into one of the ports of the X-ray tube and further by two small steel plates with slits 3/32-in. wide and 1/2-in. long placed in front of the window of the Geiger-Mueller (G-M) tube. One of the plates was located 1/2 in. and the other 2 1/2 in. from the window of the counter; both plates were contained in an aluminum holder mounted on the box containing the G-M tube. This type and degree of collimation should eliminate any intensity due to scattered radiation; the transmitted intensity would then be solely a functior. of the absorption by the suspension at that level. Experimentally, homogeneous suspensions of finely ground quartz were prepared, Daxad (a sulfo-nated compound made from wood) was added as dis-persant, and the transmitted X-ray intensity measured as a function of time at a fixed depth in the suspension. In more detail, the experimental procedure involved the following: 1) measuring the transmitted X-ray intensity through the Daxad solution at a predetermined position or settling depth in the absence of solids, 2) placing a known amount of dry solids into the vessel and agitating thoroughly, 3) measuring the transmitted X-ray intensity at time zero (i.e., immediately upon cessation of stirring), and 4) measuring the transmitted X-ray intensity as a function of time (a 10-sec counting interval being chosen and counting being started 5 sec before the desired time). Since a linear relationship exists between percentage solid in a slurry and the logarithm of transmitted intensity for a homogeneous material, the cumu-

Jan 1, 1961

By Oscar M. Wicken

The mineral magnesite (MgCO3) if pure would consist of 47.7 pct MgO and 52.3 pct CO2. It is one of the calcite group of rhombohedral carbonates which includes calcite (CaCO3), siderite (FeCO3), rhodocrosite (MnCO3), and smithsonite (ZnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions, whose range is still imperfectly known.* MgCO3 and FeCO3 appear to form a complete series of which breunnerite (ferroan magnesite) is a well known variety. Because of the considerable difference in size of the Ca and Mg ions, there is only a limited range in substitution in the MgCO3-CaCO3 series. (Dolomite, not strictly a member of the calcite group, may be regarded as an ordered structure developed when Ca: Mg is approximately 1:1.) The practical consequence of these relationships is that the lime carbonates (calcite and dolomite) are commonly present in magnesite deposits chiefly as mechanical mixtures. Magnesite may be either crystalline or "amorphous" (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black through shades of yellow, blue, red or gray. It is rarely found pure but generally contains variable amounts of iron, lime, and silicate minerals. Color cannot be used as an index of purity except under specific local conditions in a single quarry. In a given quarry an experienced man may be able roughly to grade magnesite by intuitively assessing such features as crystallinity and color. Crystalline magnesite occurs in larger deposits, but the cryptocrystalline variety is more common. The latter is fine-grained and compact and shows no cleavage; often it is descriptively called "bone magnesite." The fracture is usually conchoidal, and hardness is 3.5 to 5.0. It is normally white, but sometimes it is light yellow to orange or buff because of included impurities. In addition to lime and iron, which may be present in small amounts, silica may be present as inclusions of serpentine, quartz, chalcedony, or other minerals. In general, commercial deposits of "amorphous" magnesite have lesser amounts of accessory minerals than does crystalline magnesite. The specific gravity of "amorphous" magnesite is 2.90 to 3.0. Pure, crystalline magnesite has a specific gravity of 3.02, but iron carbonate, commonly present, raises the specific gravity to somewhat higher values. Magnesite dissociates, when sufficiently heated, into magnesia (MgO) and carbon dioxide. Either simultaneously or upon further heating the magnesia develops a crystalline structure identical with that of the natural mineral, periclase, which occurs sparingly in nature but not normally in workable deposits. Brucite is another magnesium mineral capable of being directly reduced to magnesia by heat alone. Brucite (Mg(OH)2) has been mined for the production of various grades of magnesia. It theoretically contains 69.1 pct MgO and 30.9 pct H2O. It may be white, but is generally blue or green with a gray cast. It has a translucent appearance. The mineral is soft (hardness, 2.5), and has a specific gravity of about 2.4. Nomenclature of Products The word "magnesite" literally refers to the natural mineral, but common usage has applied it plus a prefatory word to two other

Jan 1, 1960

By V. Koump, T. F. Perzak, R. G. Olsson

The vate of dissolutioz of carbon in molten Fe-C alloys urns studied by votating- cylindrical g-vaphite sairlples in a stationary crucible containing the melt. The rate of dissolltion was determdined from the change in the bnth co)npositiorz. Alccss-tvansfev coeffi&apos;cients, calcilated with the assurlption that the inte)yacial liquid ulas saturated with carbon, were found to be in agreement with an existing Correlation fov mass transfer jroni votating cylinders. It is corzcllrded tlat, itz the wnge of- Reynolds&apos; numbers itzvestigated (790 to 18,000), the vate of dissolutio of carborz in Fe-C alloys is controlled by tile rate of carbon difirsion from the interface. The dissolution of carbon in molten Fe-C alloys has been the subject of a number of investigations. Most of these investigations have been inconclusive because of poorly defined experimental variables. Two of the more sophisticated studies are summarized below. Dahlke and Knacke&apos; studied the phenomenon by, in part, immersing graphite rods into 0.5 pct carbon-steel for different lengths of time. Since the experiments were conducted in air or in CO atmospheres, the melt was strongly agitated by gas evolution. It was concluded that the change in bath composition as a function of immersion time was in agreement with the assumption that the dissolution process was transport-controlled. The hydrodynamic conditions in these experiments, however, were not well-defined and gave no indication of the nature of the dissolution process at higher fluid velocities. In a recent study Shurygin and ruk investigated the dissolution of carbon in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Small graphite disks were rotated in a crucible containing molten alloys under such conditions that only the lower face of the disk was exposed to the melt. The results of this investigation indicate that, over the range of velocities (100 to 1000 rpm) and bulk liquid concentrations (0.7 to 4.5 wt pct C) considered, the dissolution of carbon in the iron alloys is limited by the diffusion of carbon from the interface to the bulk liquid (a transport mechanism). For the particular geometry used by these authors, exact analytical solutions of hydrodynamic and diffusion problems are aailable. Hence the experimental results obtained by Shurygin and Kryuk permit the evaluation of diffusion coefficients of carbon in the four systems investigated. In the present investigation a series of experiments were conducted in which the rate of dissolution of carbon in Fe-C alloys was measured under conditions which permitted wide variation of the fluid velocity and the carbon concentration of the bulk liquid. Graphite cylinders were rotated at different speeds in a stationary concentric crucible containing various molten Fe-C alloys. THEORETICAL DEVELOPMENT In general, the resistance to mass transfer from a solid interface to a turbulent liquid is assumed to reside in a laminar boundary layer adjacent to the interface. If it is also assumed that the diffusion coefficient is independent of concentration, the steady-state rate of dissolution for the case of arbitrary liquid and solid densities can be obtained from the integration of the equations of continuity. The derivation is similar to that used by Lommel and chalmers4 for the case of pl = ps. The solution, expressed in terms where N = rate of diffusion of the solute from the interface. Exact analytical solutions of the hydrodynamic equation for the boundary layer thickness are available for only a limited number of geometries. Consequently, a mass-transfer coefficient, k, is usually

Jan 1, 1967