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By W. T. Turrall, M. J. Cook

A discussion of modern developments in beneficiation of fine sizes of anthracite, this paper includes a description of the plant flowsheet, an analysis of operating results, and a summary of fundamentals of mineral separation relative to plant operation. DURING the past several years Lehigh Naviga-tion Coal Co. has installed equipment at Tamaqua and Lansford collieries for cleaning and sizing No. 4 buckwheat —3/32 + 3/64 in. and for recovering and cleaning flotation coal —20 + 200 mesh at Tamaqua colliery. Papers describing some of these installations have been presented to AIME. At Coaldale colliery, however, methods used to clean fine coal were inadequate and inefficient. Management decided upon a thorough investigation of all existing processes before building a plant to treat the combined three sizes mentioned. Investigation, carried out on company property and at other plants, entailed a study of hydrotators, hydroclassifiers, tables, spirals, flotation machines, methods of screening, and methods of dewatering. On the basis of this investigation a flowsheet was designed which necessarily excluded many processes in use, and the writers wish to emphasize that no criticism is implied by omission of processes or machines. A determining factor in selection of many machines was the policy of standardizing equipment wherever possible. Flowsheet and Operational Data The first principle to be considered in designing of any plant is efficiency of cleaning as related to laws of classification. Beneficiation of coal may be described as separation of two materials having different specific gravities. Although there is an inherent ash content even in the purest coal which slightly affects its specific gravity, it is recognized that many particles are true middlings. The percentage of these particles allowable in the final product depends upon the ultimate ash, or specifications of the consumer. Richards in his study of free settling and hindered settling classification' determined that particles of equal size and different specific gravities had unequal settling velocities. He also determined a definite size relationship for equal settling velocities with free settling and hindered settling conditions. Considering the design of machines used to clean No. 4 and No. 5 buckwheat, it may be assumed that both free settling and hindered settling conditions exist and that ratio of size for practical operations is between the established values. The essential factor is that the more efficiently and closely sized the feed is maintained, the more nearly perfect the resulting separation. Flowsheet design was governed primarily by factors related to the 1200 to 1500 tons per hr feed to the main plant. It should be stressed that because of the many sources of supply from mine and stripping, the physical characteristics of this feed varied considerably. The most significant influence was varying percentage of fines, necessitating that all machines be capable of operating under maximum peak load during periods of surge. Since cleaning practice is a wet process, about 9000 gal per min containing 14 to 15 pct solids, or 350 tons per hr, must be treated. This slurry contained all the fines, or —3/32 in., but also percentages of oversize, up to 1 % in., dependent on spills or breaks in screen jackets, a not uncommon occurrence in preparation plant practice. The flowsheet developed is shown in Fig. 1. Circled numbers represent points of sampling. Table I gives operational data including size, ash by size, composite ash, rate of flow in gallons per minute, percent solids dry weight, and average tons of solids per hour. It should be noted that these results are subject to human error in sampling practice. Detailed information reported is a representative evaluation of plant operation.

Jan 1, 1954

By J. Chipman, N. J. Grant, R. Rocca

Desulphurization of liquid iron by reducing slags of the electric-furnace type was studied from 65 heats. Variations were made in basicity over a wide range and in FeO up to about 5 pct for their effects on desulphurization. The role of FeO in desulphurization from the blast furnace, to the electric furnace, to the oxidizing conditions of the open hearth is shown to fit a relatively simple pattern of behavior. THE mechanism which controls the desulphurization of molten iron by basic slags has been the object of several investigations. In particular, equilibrium determinations have been made both in the field of basic open-hearth slags, which have a high iron-oxide concentration, and in the field of blast-furnace slags which have a very low iron-oxide concentration. In both cases the desulphurization ratio has been found to increase with increasing basicity of the slags; however, the mechanism of desulphurization differs in the two cases. In basic open-hearth slags desulphurization occurs mainly as a partition of iron sulphide:&apos; FeS * (FeS) and the desulphurization ratio is approximately independent of iron-oxide concentration in the slag. In blast-furnace slags the concentration of iron oxide is very low as a result of the highly reducing conditions in which they are formed. The controlling reaction for desulphurization is then:2,3 FeS + (CaO) <=* (CaS) + (FeO) The slags of the reducing stage in the electric furnace have an iron-oxide concentration which is intermediate between blast-furnace and open-hearth slags. The study of the mechanism of desulphurization for these slags has been the object of this investigation. The importance of low (FeO) in the slag for desulphurization was first verified by Bardenheuer and Geller,& who found that high desulphurization ratios were obtained in highly reduced slags. It was recognized" hat iron oxide in the slag becomes a controlling factor in desulphurization only at FeO concentrations approximately under 5 pct. A recent investigation conducted by Buehl,7 upon the suggestion of one of the authors, confirmed this opinion from the results obtained from a heat conducted in a small arc furnace. In the present investigation, slags of very high basicity, such as often are encountered in the basic electric furnace, could not be studied, but equilibrium data have been obtained for slags in a wide basicity range. The iron-oxide concentration in these slags ranged from 0.08 to 15 pct and was controlled by the addition of silicon to the metal. Other constituents of the slags were mainly CaO, MgO, SiO2, A120,, and CaF,. The experimental technique was essentially the same as that of previous investigations.1 8-lo In an open magnesia-lined induction furnace, 65 lb of Armco ingot iron was melted. An atmosphere of hydrogen was maintained over the melt for 1 hr to bring the carbon content down to approximately 0.010 pct maximum. The bath then was exposed to air for 25 min to remove hydrogen. The electrodes were put in place, and the furnace was operated from this point on in an atmosphere of nitrogen. A synthetic slag was added to which additions of silicon and iron sulphide were made. A rate study conducted at the beginning of this investigation had

Jan 1, 1952

By W. A. Tiller, W. C. Johnston

The solute distribution ahead of an advancing solid-liquid interface is controlled by varying the momentum boundary layer thickness in the liquid adjacent to the interface. Single pass zone-melting experiments on Pb-Sn alloys are described in which the liquid is caused to rotate in the plane of the solid-liquid interface due to the influence of a magnetic .field rotating in this plane. The variation of the diffusion boundary layer thickness with field strength is determined. DURING the freezing of an alloy a partitioning of solute occurs at the solid-liquid interface, the magnitude depending upon the difference in the solid and liquid solubilities at the interface temperature. Because the diffusion coefficient is so small in the liquid relative to normal freezing rates, either a pileup or a depletion of solute occurs at the interface when the partition coefficient, kO, is either less than or greater than unity, respectively. This solute distribution is completely characterized by i) the solute concentration in the liquid far from the interface, C) the ratio of freezing velocityf, to diffusion coefficient, D, iii) the partition coefficient, ko, and iv) the thickness of the diffusion boundary layer, 6,, at the interface (this assumes that an electric field is not applied across the interface). For a particular system, C ko and D are fixed so that the character of the solute distribution can be changed only by a variation of either f or 6c. As is well known, the freezing velocity can be changed by varying the thermal environment of the alloy. Whereas, the thickness of the solute rich layer can be changed by varying the fluid flow conditions in the liquid. It is the purpose of this paper to describe a technique for controlling the fluid flow conditions in the liquid. During most solidification experiments the driving force for fluid flow arises from either mechanical mixing, thermal convection or electromagnetic mixing. The momentum boundary layer thickness, 6m at the solid-liquid interface, within which negligible movement of the liquid occurs, has been calculated for the special case of mechanical mixing where crystals are solidified by the Czochralski technique.l,2 The calculation of 6m for the case of thermal convection has also been made.3 In some calculations it has been assumed that the momentum boundary layer thickness, 6,, may be equated to the thickness of the diffusion boundary layer 6c, at the interface. However, as may be seen from Appendix I this is only true in very special cases and in general where a is a constant of magnitude determined by the particular liquid alloy. Neither calculations nor experimental data exist for the dependence of upon electromagnetic mixing. In this paper experiments are described in which the liquid is caused to rotate in the plane of the interface due to the torque developed on it by a magnetic field, H, rotating in this plane. The variation of is controlled by the variation of H. A magnetic field rotating in a plane perpendicular to the interface has been used for the purification of aluminum. Experimentally, we determined the variation of 5C with H by using the zone-melting technique of pfann5and a theoretical relationship of Burton et a1.2 pfann5 has shown that, after the passage of one molten zone through a long cylindrical charge of uniform concentration, CO, the solute distribution, C,, in the solid is as shown in Fig. 1. The equation describing this distribution is

Jan 1, 1962

By Jack L. Taylor

Single crystals of tungsten grown from powder -metallurgy swaged rod by high-temperative annealing were deformed in tetzsion at temperatures from 2500 to 5000 OF. Orientation of specittzen tensile axis, strained ratrix, and defortnation bands was determined optically by reflections from {110} etch pits. Slip traces meve analyzed and slip directiorz determined. Results indicate that {110}(111) , {112){111}. and {123}{111} type slip occur in tungsten over the terpe,atuve rutge investigated. Slip is orientation-dependent occuvring on tCuzt cowzbitzation oj slip plane and direction which has the highest critical resolved shear stvess. Overshooting appears to be a general occurrence between 2500&apos; and 5000°F. Dejornatiotz bands show rotation in a directiorz opposite to the yotation of tire tensile axis. DEFORMATION in bcc metals has been reviewed by Maddin and Chen,&apos; Keh and eissman,&apos; and most recently by Nabarro, Basinski, and olt. From these reviews it is apparent that some disagreement exists concerning the crystallography of plastic deformation in bcc metals. There is evidence of noncrystallo-graphic slip, the crystal slipping on or near a noncrys-tallographic plane in the (111) zone for which the resolved shear stress is greatest. There is also evidence to indicate that crystallographic slip occurs in the planes of the same zone. On the other hand, there is agreement that the close-packed direction ( 111) is the slip direction in bcc metals. Further, in pure bcc metals4 and alloys the operative crystallographic slip systems are strongly dependent on temperature. Both crystallographic and noncrystallographic slip have been reportede8 in tungsten, a group VIA bcc metal. The number of slip families which operate in the case of crystallographic slip, however, has been in question. The earliest study by oucher&apos; of single-crystal tungsten tested at temperatures of 1800 to 5000°F led to the conclusion that only {112)( 111) type slip operated. Raymond and eumann recently reached the same conclusion studying deformation by rolling of plasma-flame single crystals at 1800°F; however, only [loo] and [110] orientations were studied. Work at high temperatures by Leber and Pughs on tungsten and Chen and Maddin9 on molybdenum suggests that conjugate slip on nonparallel (110) planes may account for the slip on (112) and (123) planes found by others working with bcc metals. The present paper presents evidence of three families or modes of slip in tungsten in the temperature EXPERIMENTAL PROCEDURE Material. Standard microtensile specimens, 0.160 in. diam by 0.640 in. gage length, were ground from commercial powder-metallurgy swaged tungsten rod, type MK. Specimens were heated for 10 min at 5150°F or 6 hr at 5400°F in vacuum of 1 x 105 Torr or less to produce single crystals. At the lower temperature an average of two out of seven specimens heated in a group developed single crystals throughout the specimen length as shown in Fig. 1, the rest remaining wholly poly crystalline. At the higher temperature, three or four out of seven specimens became single crystal. Other than to note that Laue X-ray photographs generally showed sharp, well-defined spots, no attempt was made to assess crystal perfection or measure dislocation density. Two tungsten single crystals grown from the melt by the plasma-arc process were also used for this study.

Jan 1, 1967

By J. B. Clark, A. S. Yue

The zone-melting technique can be adapted for the de-termination of the eutectic composition in complex metal systerrzs. The application of this method is demonstrated in a simple eutectic system, Mg-AE, in which the eutectic composition is known and in a complex ternary system, Mg-Al-Zn, in which the literature is uncertain as to the composition of the ternary eutectic. The advantages and limitations of this unique approach for the determirution of the eutectic composition are discussed. ThE eutectic composition in phase diagrams is usually determined by thermal analysis of a series of arbitarily selected alloy compositions. The temperatures of the liquidus and eutectic arrests for each alloy are plotted and the eutectic composition is estimated by extrapolation to the entectic temperature of the curve formed by the liquidus arrest temperatures for the series of alloys. Although this approach readily yields the eutectic temperatures, several dekrminations are needed to estimate the eutectic composition, even in a simple system. In a complex ternary system, a great many determinations are often necessary to estimate, even approximately, the ternary eutectic composition. Thus, the conventional method is inherently tedious and time consuming. The application of zone melting provides a relatively efficient method of determining the eutectic composition.&apos; As an illustration, consider the zone melting of an alloy composition C, in the simple eutectic system A-B, shown in Fig. 1, under the ideal conditions of infinitely rapid diffusion in the liquid, no diffusion in the solid, and ease of nucleation of both phases. As the zone moves along the bar, the composition of the zone is enriched by solute rejected during the freezing of the a phase and the zone composition approaches the eutectic composition CE.Once the zone composition attains the lowest melting composition, i.e., the eutectic composition, it remains at this composition as the zone moves along the bar and finally freezes as such at the end of the bar. Chemical analysis of the end of such a zone-melted bar then should yield the eutectic composition CE of the system A-B. A corresponding analysis can be made for a ternary eutectic system. Under the ideal conditions noted above, only one pass of the molten zone is required to yield the eutectic composition. Experimentally, however, a solute-rich layer forms at the solid-liquid interface2 and the composition of the zone does not attain the eutectic composition as rapidly or as uniformly as in the ideal case outlined above. But with agitation of the melt, the ideal conditions can be approximated experimentally. Also, as shown below, zone melting permits a cumulative build-up of the solute at the end of the bar to the eutectic composition. The purpose of this paper is to demonstrate this unique method for determining the eutectic composition. The method is here applied to two systems: first, to the binary Mg-A1 system, in which the composition is well established, and second, to the complex Mg-Al-Zn system in which there is doubt concerning the composition of the ternary eutectic. EXPERIMENTAL PROCEDURE The zone-melting apparatus used in this study is described in detail elsewhere.3 Briefly, the binary alloy rods (5/8 in. in diam and 9 in. long) and the ternary alloy rods (5/8 in. in diam and 6 in. long), with the compositions given in Table I, were zone

Jan 1, 1962

By N. J. Grant, B. C. Giessen, R. Koch

The system Nh-Ir was investigated over the complete concentration range by metallography and X-my techniques, using forty one alloys. The solubility limits of terminal and intermediate phases and the solidus temperatures were determined. Five intermediate phases were found: a Nb3Ir, cubic, Cr3O type; tetragonal, ofecr thorhomhic, isostruc-turn1 with (ta-Rh); and a Nhlr3. cubic, AuCu, type. a Nb3lr and a Nbfr3 melt congruently; three eutectic and three pentectic reactions occur. The phase diagram of the Nb-Ir system had not been fully treated in the literature; only surveys of intermediate phases were found.1"5 In this study, the details of the phase boundaries were investigated as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS The experimental procedures such as arc melting of powder compacts, heat treatments, solidus measurements, X-ray, and metallographic observation were identical with those used in the work on the Nb-Rh phase diagram.&apos; They will therefore not be repeated here except where the conditions differed. The purity of the niobium powder was as stated in Ref. 6; the iridium powder of 99.9+ pct purity from J. Bishop and Co., Malvern, Penn., did not contain impurities exceeding 100 ppm, except rhodium (200 ppm). The melting points and vapor pressures of both elements are very similar. This fact contributed to a very small weight loss on melting and facilitated preparation of homogeneous alloys. As shown in Ref. 6 for Nb-Rh, no oxygen pick-up exceeding 200 ppm had to be considered; this was regarded as valid also for Nb-Ir. A total of forty one alloys were used in the determination of the phase diagram; their concentrations are shown in Fig. l, which presents the phase diagram. The concentration limits as determined by the weight-loss method averaged <0.2 at. pct, and never exceeded 0.5 at. pct. Heat treatments were carried out as described in Ref. 6. Depending on the concentration, only tantalum, tungsten, or iridium containers were employed, avoiding oxide crucibles altogether. Alloys from 0 to 25 and from 65 to 100 at. pct Ir were homogenized at 2095°C for 15 hr, intermediate compositions from 25 to 65 at. pct Ir for 65 hr at 1780°C. A typical annealing-time schedule is presented in Table I. Solidus points were measured as described in Ref. 6 with the modification that samples rich in niobium were held between pieces of tantalum foil and samples of high iridium concentrations were held between rhenium platelets or in iridium wire. After each run it was ascertained metallographically that no reaction with the holder had occurred. Rhenium was selected as holder material after it had been shown in separate tests that the melting points of Re-Ir alloys rise continuously from 2440°C. Metallographic examination was carried out as described in Ref. 6, and the same procedure and etchants were used successfully. While metallographic discrimination between a Nb3lr and o was easily possible, X-ray diffraction was necessary to separate al and ct2. X-ray powder patterns were taken and evaluated as for Nb-Rh6 yielding the error limits indicated in Table 111, to be introduced later. For the determination of the invariant reactions and phase boundaries, the same techniques as for Nb-Rh6 applied. The general accuracy of invariant concentrations is regarded as somewhat higher than for Nb-Rh due to the small slope of most solvus lines.

Jan 1, 1964

By L. E. Mannion

Sodium carbonate or soda ash is one of the two principal alkalis of commerce, the other being sodium hydroxide. The use of sodium carbonate is recorded in ancient Egypt, where naturally occurring brines or solid salts were the source of impure soda for glass manufacture. In early modern times until the 19th century, soda ash, as well as potash, was recovered mainly by leaching the ashes of plants. In Europe, during the 18th century, a brown lye for laundering was produced by pouring hot water over burned seaweed. One of the better grades of this kind of material was a product from Spain termed "barilla," which analyzed 24 to 30% Na2CO3 (Hou, 1942). The birth of the modern chemical industry may be said to start with the LeBlanc process for making sodium carbonate from salt, sulfuric acid, and lime. Although invented in France in 1691, England made the most extensive use of it. In 1863 Ernst Solvay devised the ammonia-soda or Solvay process, and by 1874 the first of many Solvay plants was built. These were to supplant the LeBlanc method and dominate soda-ash production until the present time. Although of lesser importance, natural sodium carbonate deposits continued to support operations in various parts of the world. Shortages during World War II stimulated production of "natural" soda ash, particularly at Searles Lake, Calif., and at Lake Magadi, Kenya. Within the last ten years in the United States, a notable surge in production has occurred based on the vast trona deposits in Wyoming. Table 1 lists some principal producers of natural soda ash and the character of the source deposits. Uses and Specifications Sodium carbonate (Na2CO3) is a white, crystalline hygroscopic powder, an aqueous solution of which is strongly alkaline. Most commercial soda ash is a product that must meet high standards of purity and uniformity. Two forms are commonly sold: a fine, powdery material called light ash, and a more coarsely crystalline dense ash; these weigh 32 to 39 and 60 to 66 lb per cu ft, respectively. Dense ash may be produced by adding a little calcium chloride to the sodium carbonate solution to control crystal size and prevent agglomeration. Specifications and typical analyses of light and dense ash in the United States are shown in [Table 2]. Sizing generally achieves about 75% of light ash and 90% of dense ash between +30 and -100 U.S. screen mesh. World use of sodium carbonate now exceeds 24 million tpy, of which the United States produces more than 7 million tons. The market for soda ash is dominated by the glass industry, which uses almost half the supply. Inorganic chemicals, including phosphates and silicates, consume about 30%. Other principal uses include the manufacture of soaps and detergents, petroleum, caustic soda, organic chemicals, and paper; and nonferrous and ferrous metallurgy. [Fig. 1] shows the percent consumption by use of soda ash in Europe, Japan, and the United States. The price of soda ash in the United States remained relatively stable during the 1960s at about $33 per ton; in 1972 it reached $35 per ton. The price in 1975 was $42 per ton. Geology Mineralogy [Table 3] is a list of the more common sodium carbonate-bearing minerals. Anhydrous sodium carbonate is almost never found in nature; only natron, thermonatrite, and trona have been used directly as sources of sodium carbonate. At Searles Lake, burkeite and hanksite are important in the reconstitution of

Jan 1, 1975

By P. F. Gnirk, J. B. Cheatham

The results of combined analytical and experimental studies involving simulated multiple bit-tooth penetration into mck are incorporated into a drilling rate equation for roller-cone bits assuming rather idealized downhole conditions. In particular, it is assumed that the rock behaves statically in a ductile fashion during bit-tooth penetration and that the rock chips are instantaneously removed from the bottom of the drill hole. The general analysis demonstrates an application of plasticity theory for the rock/bit-tooth interaction to the formulation of an upper limit on rotary drilling rate. INTRODUCTION Extensive experimentation involving single and indexed bit-tooth penetration into rock in a confining pressure environment has demonstrated that the chip formation process is of a ductile, or pseudoplastic, nature at sufficiently low differential pressures so as to be of interest in rotary drilling. Coincident with the experimentation, analytical consideration has been given to the theoretical problems of single and indexed bit-tooth penetration into rock. In general, the analyses have assumed that the rock behaves statically in a rigid-plastic fashion and obeys the Mohr-Coulomb yield criterion. The quantitative comparison between experimental and calculated values of bit-tooth load required for chip formation has been remarkably good for a variety of rocks commonly encountered in drilling and at simulated differential pressures as low as 500 to 1,000 psi. Results obtained recently for indexed bit-tooth penetration indicate that the work (or energy) required to produce a unit volume of rock chip can be minimized by a proper combination of bit-tooth spacing and bit-tooth load for a given rock type and differential pressure. By utilizing this information, it is possible to formulate a drilling rate equation, at least in a preliminary fashion, for a roller-cone bit performing under rather idealized downhole conditions. In particular, through the use of characteristic dimensionless quantities pertinent to a roller-cone bit and to indexed bit-tooth penetration, interrelationships among bit weight, rotary speed, rotary power, bit diameter, rock strength and bit-tooth shape and spacing can be explicitly expressed. In the formulation of the equations, however, it is assumed that the rock chips are instantaneously removed from the bottom of the drill hole and- that the rock behaves in a ductile manner during bit-tooth penetration. In addition, the effects of bit-tooth load application and penetration by a yawed tooth at an oblique angle are neglected. Although the analysis is presented in the light of some rather restrictive conditions, it does demonstrate a method of applying fundamental rock/bit-tooth interaction data, obtained by combining the results of analysis and experiment to the formulation of a drilling rate equation for rotary drilling. JNDEXED BIT-TOOTH/ROCK INTERACTION PREVIOUS RESULTS The mechanics of bit-tooth/rock interaction under simulated conditions of borehole environment have been extensively described in a number of papers.l-ll In particular, the effects of differential pressure, mechanical properties of rock, pore fluid, bit-tooth shape and spacing, rate of bit-tooth load application and dynamic filtration below the bit-tooth have been investigated experimentally. From a sequence of experiments.1-4 it was demonstrated that, for dry rock at atmospheric pore pressure, the mode of chip formation exhibits a transition, with increasing confining pressure, from predominantly brittle to predominantly ductile. This transition

Jan 1, 1970

By Wieland D. R., Hurst R. E., A. R. Hendrickson

Analysis of acidizing techniques, in correlation with reservoir data and a backlog of past treatments, has resulted in the development of a valuable engineering guide for planning acidizing treatments. Such treatments fall into three categories: (I) acid injection into the pores of the matrix; (2) acid injection into natural formation fractures at less than parting pressure; and (3) combination acidizing-fracturing treatments in which acid solutions (without propping agents) are injected at treating pressures sufficient to open and extend fractures through which the acid flows. Because the spending tirnze of acid during a specific well treatment does not change appreciably, maximunl penetration is attained when the first increment of injected acid is completely spent. Additional acid injection cannot be expected to further extend the benefits of the treatment. Depth of penetration will depend upon the reaction rate of the acid under treatment conditions, the injection rate of the acid into the matrix or fractures and the area-volume relationship existing in the flow channels. Based on Darcy&apos;s flow formula, extremely low injection rates must be used in order to keep bottom-hole injection pressures below formation fracturing pressure. As a result, only limited penetration of unspent acid will occur. Treatment records indicate that, in most acidizing treatments, formation parting pressures are exceeded, greatly extending acid penetration. Under these conditions, stimulation benefits are limited to the fracture area produced during the spending time of the first increment of acid injected into the formation. This area may be calculated from laboratory and well data to estimate depth of penetration. This, in turn, may be correlated with productivity data to assist The art of gas and oil well acidizing has been characterized by many changes in treating materials and techniques since its inception. These developments have been designed to provide greater production increases. prolong production declines and shorten payout time. Such improvements have been based primarily on data derived from laboratory research and field experience. As more of the variables influencing these treatments have been recognized and evaluated, acidizing has become less of an art and more of a science. Recent studies of fracturing treatments,&apos; in light of individual well conditions and the results of thousands of fracturing treatments, made possible the formulation of an engineering guide that is now being used to select optimum treating techniques and to forecast probable results of such treatments. A similar analysis of the factors controlling acidizing treatments has been made and is the basis for this paper, The findings herein can be used as a guide in the selection of acidizing solutions and techniques, tailored to fit specific well conditions and to provide optimum stimulation per dollar cost. Acidizing treatments may be classified into three basic categories—(1) treatments in which the acid is injected uniformly into the pores and flow channels of the matrix, (2) treatments in which the acid enters natural fissures and fractures in the formation at less than fracturing pressures and (3) injection of acid into the formation at a pressure sufficient to open and extend fractures into the rock through which the acid penetrates (without the inclusion of a propping agent). TYPE 1 — MATRIX ACIDIZING This category consists of treatments in which acid solutions are injected into a homogeneous carbonate

By E. J. Efsic, C. M. Wayman

The fcc to bcc y to a transformation in an Fe-24.5 at. pct Pt alloy was studied and found to be martensitic. Large martensite plates are formed in this alloy which are ideal for crystallographic studies; the Ms temperature is about -5°C. Ordering of the parent phase prior to transformation to martensite causes a pronounced lowering of the Ms temperature. For the first time in the case of alloys of iron, measurements of the habit plune, orientation relationship, and magnitude and direction of the shape stvain have been obtained on preselected martensite plates. It is shown that by measuring the initial and displaced (as a result of the shape strain) positions of three or more non-parallel fiducial scratches on one reference surfice the maguitude and direction of the shape strain and the state of distovtion at the parent-mavtensite interface can be determined with a reasonable degree of accuvacy. The agreement between the phenomenolog-cal crystallographic theory of martensitic transformations and the experimental results habit plune, orientation relationship, and nlagnitude and direction of the shape strain) is essentially perfect, and is thought to be the best reported to date for iron alloys. THE comparatively few investigations on binary Fe-Pt alloys have been concerned with magnetic properties, ordered phases, and the equilibrium diagram itself. Various investigations have shown that the equilibrium diagram is of the open y field type; in addition there is a peritectic transformation, a minimum melting point, and three ordered phases: Fe3Pt, FePt, and FePt3. The results of a number of investigators1-6 have shown that the temperature dependence of the y to a (and reverse) transformation in iron-rich alloys is reasonably well-established. The Fe3Pt phase was first noted by Kussman and Rittberg,7 and its existence was later confirmed by Franklin et al,8 Steijn and Donahoe,9 and Berkowitz et al.10 The FePt phase was reported by Isaac and amman&apos; and later confirmed by a host of others.3,6,7,12,13 Kussman and Rittberg7 noted the existence of the superlattice FePt3. Prior to 1956, the 1 to a transformation in iron-rich Fe-Pt alloys was termed "irreversible". In 1957 Klokholm and Donahoe" termed this transformation martensitic, presumably because of its occurrence at temperatures well below those where diffusion normally takes place. This observation served as a point of departure for the present investigation, and in the very early stages of the work to be discussed it was readily verified that the y to a transformation in iron-rich Fe-Pt alloys is indeed martensitic. Quite large martensite plates exhibiting the well-known surface tilt were observed. These plates are ideal in the sense that the boundaries between the parent and product phases were usually very straight. It thus appeared that Fe-Pt martensites would be ideal for crystallographic studies, and this was the purpose of the present investigation. Details of the crystallography of martensitic transformations (particularly for iron alloys) and the phe-nomenological crystallographic theories15-l7 have been discussed many times and thus will require very little elaboration here. The end result of these theories, given in matrix form, is

Jan 1, 1968

By J. T. Dewan

An experimental setup is described whereby the responses of Neutron logging instruments have been determined opposite formations of different porosities and under various borehole conditions. The results of these tests are presented in several charts which show how the Neutron log is affected by the following factors: hole diameter, casing, cement, salinity and weight of drilling mud, and position of logging tool with respect to the wall of the hole. The responses in the case of empty holes are also shown. A chart is furthermore presented which shows the shapes of the Neutron log, as a function of logging speed and time constant, at the boundaries between two formations with different porosities. These were derived mathematically using as a basis laboratory determination of the shape of the curve under static conditions, i.e. at very low logging speed. Corrections for the readings made opposite thin beds are given by these computations. The correction is found negligible under usual logging conditions for beds thicker than about 4 ft. INTRODUCTION The Neutron log is used in borehole surveys both for the delineation of porous formations and for the quantitative estimation of their porosities.1,2,3,4,5 It is common practice to calibrate the response of the Neutron log in terms of porosity values for each given geological unit by means of empirical comparisons between the deflections of the neutron curve and the porosity values given by the core analysis in a sufficient number of wells. Usually, the plots of the porosity values vs Neutron log deflections show a definite trend. It is therefore possible to trace an average line across the plotted points. This average line constitutes a calibration curve which can be used to evaluate the porosities from the Neutron logs in the other wells drilled in the same region. Futhermore, when the porosity values are plotted on a logarithmic scale and the Neutron log deflections on a linear scale, the calibration curve is practically a straight line. Accordingly the calibration curves are often determined by simply tracing a straight line between two points corresponding to two widely different porosities. Different choices are made for these two points, depending on local conditions. For example, one point will be defined by plotting the deflection of the Neutron curve opposite a formation known to be very tight, for which an average porosity value of 1 or 2 per cent is assumed. The other point may correspond to shale sections, to which a porosity of around 40 per cent is ascribed. The information provided by the eletrical logs — in particular the Laterolog, Limestone log or Micro-Latero-log — is also very often a help in the calibration of the Neutron logs. Empirical approaches such as these make possible the derivation of fairly reliable porosity values from the Neutron logs in many cases, at least in open holes and in essentially clean formations. There are, however, several causes of uncertainty which may sometimes entail appreciable errors. On the one hand, the Neutron log readings are influenced by the borehole conditions: hole diameter, presence or absence of casing and cement, presence or absence of drilling mud, characteristics of the mud, and position of the logging instrument with respect to the wall of the hole. The amplitudes of the curves opposite thin beds are furthermore atfected by the bed thickness,

Jan 1, 1957

By H. I. Aaronson, C. Laird

Cold rolling by 50 pct a A1-4 pct Cu alloy containing many 0&apos; plates has been found to accelerate markedly the transformation of 8&apos; to 0 upon further aging. Although the basic mechanism of this transformation remains unchanged by plastic deformation, the nuclea-tion kinetics of 8 become appreciably more rapid and also less dependent upon temperature. Particularly at lower aging temperatures, rounded idiomorphs replace several faceted rnorphologfes. The rates of growth of 9 idiomorphs in deformed specimens aged at 300°C are appreciably more rapid than simple volume diffusion control allows. This observation is shown to be explained by an excess vacancy, rather than by a dislocation Piping mechanism of growth. ThE rather complex phenomenology of the 8&apos; —8 transformation in Al-Cu alloys has been recently elucidated in considerable detail by means of transmission electron microscopy.&apos;-4 This technique was also employed in the present investigation in order to examine the effects of plastic deformation upon the transformation of 8&apos; to 8. The mechanism of the transformation in undeformed Al-Cu alloys has been established as the following sequence of events.1"4 The first step is the nucleation of 9 at (Y:8&apos; boundaries. Nucleation of a 0 crystal takes place, however, at only a very small proportion of the 8&apos; plates present. Each 0 crystal simultaneously consumes the host 8&apos; plate and the a! in the immediate vicinity, with growth into a being the rate-controlling process. The remaining 8&apos; plates are then dissolved as they fall under the concentration shadow of the growing 8 crystals. The evidence on the effects of plastic deformation upon these processes is intriguing, but much less detailed. The careful X-ray studies of Graf and Guinier have shown that the aging times required to form detectable amounts of 8&apos; and 8 are reduced by prior cold working. Thomas and Nutting confirmed these results by replication electron microscopy. Nile-shwar,* on the other hand, reported that creep deformation decreases the rate of formation of 0. While this difference may have been caused by the use of concurrent rather than successive deformation and ag- ing, the X-ray technique which he used was able to monitor only the 0 phase. It is thus possible that the times needed to form 8&apos; were increased moreg than the kinetics of 8&apos; — 8 transformation were accelerated. At 90 pct deformation by cold rolling, Graf and Guinier found that the usual 0&apos; —0 8 sequence is reversed: 0 forms first. von Heimendahl 10 confirmed this result with transmission electron microscopy. Pollard and Nutting, 11 and more recently Driver and Barrand, 9 having used the same technique, report that 9 also forms first during creep deformation. In the present study, the maximum amount of deformation was limited to 50 pct reduction by cold rolling in order to insure that 8 formed principally by the decomposition of . I) EXPERIMENTAL PROCEDURES This investigation was conducted on an Al- 3.93 pct Cu alloy, prepared as previously described. 4 Morphological and crystallographic effects of plastic deformation were studied in specimens annealed 6 hr at 548°C, quenched, and then aged for either 3 or 8 hr at 250°C to form large numbers of 0&apos; plates. After cold rolling to a 50 pct reduction in thickness, the

Jan 1, 1969

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of- liquid Mg-Pb allojs have been determined by an isopiestic method from 18 to 42 at. pct Pb and by a thevmodynumic analysis of the phase diagram frofiz 0 to 100 at. pct Pb. In the overlapping composition range the magneszupn activity values derived by the two methods are in excellent agreement, thus mutually supporting the correctness of the Mg-Pb phase diagram previously determined by the authors and of the acticitzes deriz~ed isopiestically. SEVERAL studies have been made of the thermody-namic properties of liquid Mg-Pb alloys. Wagner and Engelhardt,1 Lantratov,2 Knappwost,3 Sryvalin et al.* and Wilson5 used the electromotive-force method, Scheil and Wolf8 and Schmahl and Sieben" applied the transpiration technique, and the present authors8 utilized the phase diagram to determine the activity of magnesium in the Mg-Pb system. The results of these studies are not in very good agreement and could not be incorporated into a general systematic analysis of the thermodynamic properties of the homologous series of the Mg-Group IV B systems Mg-Pb,8 Mg-Sn,° Mg-Ge,10and Mg-Si.11 The thermodynamic properties of the Mg-Pb system were therefore re investigated by an isopiestic technique which has been developed for similar studies in the Mg-SnB and Mg-Ge10 systems- Lead specimens, contained in iron or graphite crucibles, were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure to form alloys of compositions which depended on their temperatures, the temperature of the magnesium vapor source, and the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE Magnesium (Dominion Magnesium Ltd., Toronto, Canada) of 99.99+ pct purity and lead (American Smelting and Refining Co.) of 99.999 pct purity were used. In the early experiments, Runs 2 and 3, the alloys were contained in uncovered high-purity iron crucibles. Alloys formed in the uncovered iron crucibles had to be chemically analyzed owing to the slight volatility of lead under the imposed experimental equilibration conditions. The compositions of these alloys were determined by a gravimetric analysis of lead as lead chromate. To avoid this problem, the remaining runs were made in covered graphite crucibles machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non- i reactivity of graphite with lead and magnesium has been previously established,&apos; and the experimental procedure has been described in full detail.&apos; In the runs using covered graphite crucibles it was found that the weight increases of the crucibles and their contents after equilibration equaled the magnesium contents of the alloys within the accuracy of the chemical analysis (i0.3 at. pct Pb). Clearly, the small lid openings of the graphite crucibles prevented significant lead losses during a run, and the weight increase was therefore taken as the magnesium content of the alloys. EXPERIMENTAL RESULTS At thermodynamic equilibrium the magnesium partial pressure of the specimens equaled that of the reservoir. Since the magnesium reservoir was always maintained at the temperature minimum of the system, the activity of magnesium of any specimen was given by the ratio of the magnesium reservoir pressure to the vapor pressure of pure magnesium at the specimen temperature. The standard state was chosen as liquid magnesium and the vapor pressure of liquid magnesium

Jan 1, 1968

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

By J. N. Anderson

Developments in reverberatory furnace practice at Noranda over the period 1928 to 1953 are described. Features of interest are increasing furnace tonnage from 700 to 2000 tons per furnace day, the use of the suspended basic roof, and improvements in furnace fuel ratio. Points of comparison and contrast between Canadian and American furnace practice are given. OPERATIONS at the Noranda smelter have been described in a series of papers published between 1930 and 1945.1-4 In the present paper the development of reverberatory furnace practice over the 25 year period from the beginning of operations up to the present time will be reviewed and current furnace practice will be described in some detail. Particular attention will be given to those features which are characteristic of Canadian practice: first, the use of the suspended basic roof; second, the deliberate driving of furnaces to give tonnages in the range of 1400 to 2000 tons of solid charge per furnace day; and third, the continuous operation of furnaces at high tonnage for many years without any extended shutdown for repairs or rebuilding. Finally, points of comparison and contrast between reverberatory furnace practice in Canada and the United States will be discussed. The Noranda smelter, which started in December 1927, was built for the reduction of ore from the Horne mine where early development had shown a comparatively small tonnage of rich cop-per-gold ore of a grade and character which would require direct smelting. The smelter was designed for a capacity of 1000 tons of ore a day and originally consisted of eight roasters, two reverberatory furnaces, and two converters, together with necessary auxiliaries. The discovery of a large new body of ore in 1928 made it necessary to increase both the size and the scope of the reduction plant. A mill which was ultimately brought to a capacity of 3000 tons a day was built for concentrating low grade ore and in addition the capacity of the smelting plant had to be greatly expanded, so that for the next fifteen years every effort in the smelter was directed toward achieving maximum tonnage. Because the layout and design of the smelter made it impracticable to add a third furnace, it was necessary to increase the tonnage on the two original furnaces by improvements in furnace design and operation, roasting and converting equipment being added as required to meet the demands of increased furnace capacity. The smelter tonnage, which reached a peak in 1941, was curtailed in 1944 when it became necessary to operate on a one-furnace basis because of a reduction in the output of the Horne mine due to a shortage of labor. Two-furnace operation at a moderate tonnage was resumed in 1949. In the early years the smelter tonnage was made up almost entirely of Noranda ores and concentrates. However, since 1937 an increasing tonnage of ores and concentrates from other mines has been treated in the smelter. In recent years, with decreased production from the Horne mine, copper concentrates from several mines in the district, treated on a custom basis, have formed an important part of the smelter tonnage. A review of developments in reverberatory furnace practice at Noranda falls naturally into the following four periods: 1—1928 to 1935, the early years; 2—1935 to 1944, the period of greatest change and development; 3—1944 to 1949, one-furnace op-

Jan 1, 1955

By C. S. Matthews, M. J. Fischer

Distortions caused by dip on five-spot sweep pattern were determined by visual experiments on a model composed of parallel plates of glass with holes drilled at the well positions. This model war designed to simulate a reservoir depleted of its primary oil and containing a gas phase. Prior to interference, it was found that the injected fluid took a nearly circular shape about the injection well for the cases studied. However, these circles moved down-dip considerably under the influence of gravity. It was concluded that pattern flooding should be practical for many dipping reservoirs. A quantitative measure is given of how much the well position should be altered to allow for dip. Experimental deternzinarions of injectivity showed this to be about the same in a dipping reservoir as in a horizontal one. INTRODUCTION This investigation was undertaken at the suggestion of the Pacific Coast area, Shell Oil Co., where a pilot water flood in a dipping reservoir was being carried out at the time this paper was in preparation. Prior to the undertaking of this flood there had been considerable speculation as to how gravity would distort a flood pattern in a dipping reservoir. The thought was expressed in some quarters that a five-spot flood would not be applicable to a dipping reservoir because the flood pattern would elongate in the direction of dip and would never form a "seal" around each five-spot. If the flood pattern elongated sufficiently, both the oil and the water might flow largely downdip rather than into the pattern producers. In view of the importance of the California water floods, it was deemed important to determine the effects of gravity on a five-spot pattern in a dipping reservoir. Previous work had also been carried out in this laboratory,1 but only for the single-fluid case. The present investigation extends these results to multifluid cases. Several sets of pictures of flood fronts are presented so that the process can be visualized. From these pictures, curves are obtained which show the correct drilling position for achieving equal times of oil-bank breakthrough. Several injectivity curves are also presented which may aid in prediction of injection rate. ASSUMPTIONS The present results were obtained with a model composed of two parallel plates of glass spaced about 1 mm apart. When the inertial forces are small, as in these experiments, the flow between the plates follows Darcy&apos;s law and is analogous to flow through porous media. In using these plates, it is not possible to scale effects of capillarity correctly as regards a transition zone between injected and displaced fluid. Calculations show, however, that effects of such capillarity should not be important in determining the gross flooding pattern in the field. In fact, in this model the capillary forces tend to circularize the pattern to a greater degree than in the field. To preserve a large ratio between the viscous forces and the circularizing capillary forces in the laboratory model, viswus glycerine was used as the flooding liquid and the rate of flooding was very high. The circularizing force is believed negligible in these experiments. In addition to the effect of the surface tension y, which tends to circularize the pattern, another capillary force must be considered. This is the adhesion tension y cos, which acts at right angles to the circularizing term y. If the plates in the model are "wetted" the same all around the periphery, then the adhesion tension,

Jan 1, 1957

By L. B. Gittinger

Sulfur is a nonmetallic element widely distributed in nature. It constitutes 0.06% of the earth&apos;s crust but only a very small portion occurs in sufficiently concentrated amounts to justify mining. Sulfur occurs in practically all animal and plant life. It constitutes approximately 0.09% of the elements in the oceans; it has been found in meteorites. Sulfur was known and used by man before recorded history. The American Chemical Society approved spelling for the element is sulfur. The English spelling sulphur is used commercially in the United States. In ancient times, sulfur was called brimstone, literally "burning stone." Today the term brimstone is used interchangeably with the term elemental sulfur. Sulfur is found naturally in the elemental form in subsurface deposits associated with gypsum and anhydrite in salt domes and sedimentary formations in evaporite basins and in solfatara-type deposits associated with volcanoes and mineral springs. Sulfur occurs also in molecular combination in ferrous sulfides (pyrites and pyrrhotite) and nonferrous sulfides (copper, lead, zinc, and nickel), and in mineral sulfates (gypsum and anhydrite); as hydrogen sulfide contaminant in natural gas; as organic compounds in crude oil and tar sands; and as pyrite and organic compounds in coal and oil shales. Sulfur resources are abundant and exist throughout the world but the extent to which they can be classified as reserves is greatly circumscribed by prevailing prices and technology. Estimates of world sulfur reserves are compiled by the U.S. Bureau of Mines. A compilation of reserves by area and source of sulfur published in 1970 and presented here as [Table 1] totaled 2.47 billion tons (Lewis, 1970). The effect of the decline in prices which has occurred since the earlier estimate is dramatically illustrated by the 1972 estimate of the U.S. Dept. of the Interior which shows world sulfur reserves of only 1.2 billion tons (Anon., 1972d). Sulfur is produced commercially from one or more sources in nearly 70 countries of the world. World production of sulfur in all forms totaled 41.6 million tons in 1971. (Sulfur statistics given in this chapter are long tons.) Native deposits, sulfides and oil and gas contributed, respectively, 31, 41, and 25% of world production (Table 2). Of the sulfur produced from native deposits, salt domes accounted for 54% and evaporite basin deposits, 44%. Volcanic deposits are of little significance except for local consumption. The past two decades have seen important shifts in the world&apos;s sulfur sources. In 1950, native deposits and sulfides each supplied about one-half of the world&apos;s production. During the 1950s, sulfur recovered from oil and natural gas grew rapidly, representing about 10% of the total by 1960. Since then, the petroleum industry has continued to increase its relative importance as a source of sulfur, representing more than 30% at 1972 year-end. Sulfur is generally classified as elemental or nonelemental for statistical purposes. Elemental sulfur is sulfur produced in the pure, uncombined form. It includes production from native deposits, as well as that recovered in the elemental form from oil and natural gas or other sulfur-bearing materials. When produced from other than native deposits, it is generally referred to as recovered elemental sulfur. Nonelemental sulfur is that which is utilized commercially in molecular combination with other elements, such as sulfides or sulfates. Elemental sulfur is being produced from salt dome deposits in the Gulf Coast region of the United States and the Isthmus of Tehuantepec in Mexico, and from evaporite basin deposits in west Texas, Poland, Sicily,

Jan 1, 1975

By A. G. Worthing

Black: Bodies.-In the ordinary conception, a black object is an opaque object that reflects but little of the light that is incident on it. This means naturally that such an object is a good absorber of luminous radiation. The black body; which is so closely connected with high-temperature measurements, represents the limit in blackness of all black objects. It is a body that not only absorbs all visible radiations but also all other radiations in the infra-red and the ultra-violet regions of the spectrum which are incident on it. No substance is known that is completely black; platinum black, one of the nearest if not the nearest representative of the ideal, reflects 1 per cent. or so of ordinary visible radiation. The closest approach to the ideal is a small opening in the wall of a relatively large opaque cavity. Any radiation incident on this black body will be almost completely absorbed if the relative dimensions are properly chosen no matter what the material may be. The great difference between the blackness of such a cavity and of lampblack, for instance, will be apparent to one who makes the simple test. Non-black Bodies.-The field of non-black bodies covers all real bodies. Their characteristics are extremely varied. So far as absorption of radiation-is concerned, these bodies range practically from the almost completely black, platinum-black, and lampblack, which absorb all but a fractional part of 1 per cent. or so of the incident radiation, by an infinite variety of steps to freshly polished silver, which ordinarily absorbs only a few per cent. The exact percentage absorbed depends not only on the nature of the incident radiation, but also on the temperature of the body, the condition of its surface, the angle of incidence, the nature of the surrounding medium, and on certain other less important conditions. As consequences of these varied characteristics, we have not only the differences of color of ordinary objects, but also the changes of color that any one object undergoes on heating or when lighted front various directions. This complexity of the phenomena, in a way, is responsible for the meagerness of knowledge, regarding materials at elevated temperatures. Measurement of High Temperatures.-Excepting in cases where the thermocouple or the gas thermometer are applicable, in which case the temperatures obtained are true temperatures regardless of-the material" studied, high, temperatures are almost always, if not always, determined from measurements of radiation. In fact, determinations of temperature from this latter point of view are often so much more convenient than the thermocouple and especially the gas-thermometer determinations that, in the region where all of these types of measurements may be made, the radiation measurements are often preferred. This is true even though the temperatures usually thus directly determined are not the actual temperatures, a consequence of the sources of the radiation being non-black bodies; in other words, a consequence of being concerned with iron, or glass, or tungsten instead of small openings leading to relatively large-cavities uniformly heated. Coordination of Experimental Results.-In order that data on iron, glass, tungsten, or other non-black bodies obtained in one laboratory, may be, correlated with similar data obtained elsewhere, temperatures must be expressed on a common scale. The true temperature scale is the natural scale for this purpose it is ordinarily the scale to which all other temperatures can be most directly reduced. When the measurements depend on the radiation, a knowledge of emissive powers repre-

Jan 9, 1919

By D. G. Westlake

Resistance was measured as a function of temperature, 77° to 350°K,for niobium with hydrogen concentrations up to 3.76 at. pct. Cooling curves exhibited a discontinuity in slope that was attributed to the initiation of hydride formation. A thermal hysteresis was explained in terms of diffusion and the effects of mechanical constraint on nucleation and growth. The heat of solution of hydrogen in saturated Nb-H solid solution was 2. 737 * 0.045 kcal per g-atom, including an unknown stress contribution. The critical ternperatures for hydride formation during cooling and for embrittlement are correlated but not coincident. This, too, has been explained in terms of mechanical constraint and stress-itlduced tratzsfomtation. Nb-H alloys undergo a ductile-brittle transition with decreasing temperature.&apos;-3 Similar behavior has been noted for v-H.1,5 For the latter system, there is evi-dence6 suggesting coincidence of the temperature of minimum ductility and the critical temperature T, for initiation of metal hydride precipitation during cooling. A decrease in ductility due to the presence of brittle hydride particles is readily explainable. The fact that ductility begins to decrease at some temperature higher than T,4,5 has led us6 to suggest that precipitation may be strain-induced locally during tensile testing. Wood and Daniels&apos; have reported that a plot of temperatures for 10 pct reduction in ductility vs hydrogen concentration in niobium is not coincident with, but parallels, the solvus.7,8 They believe this indicates a correlation of precipitation and embrittlement. Unfortunately, the two reported solvuses 7,8 to which Wood and Daniels refer are not in agreement with each other. Furthermore, neither solvus was determined experimentally: each was a plot of calculated solubilities. Thus. neither is highly dependable for determining whether embrittlement coincides with initiation of hydride precipitation. Longson 9 studied phase relations in the Nb-H system between 77° and 473°K by dilatometry. Comparison with metallographic observations convinced him that discontinuities in the slopes of his dilatometric plots were coincident with the initiation of hydride precipitation. Plotting the logarithm of the hydrogen concentration vs the reciprocal of the temperature at which precipitation was initiated during cooling, he obtained a straight line shown in Fig. 1. Walter and chandler,&apos;&apos; using X-ray techniques to detect the for mation of a second phase? have obtained three experimental points in the temperature range 295° to 338°K which fall within Longson&apos;s experimental error for this plot. A similar plotg of temperatures at which dissolution was completed during heating was a parallel line shifted toward higher temperatures. A straight-line plot was obtained, also, for the temperatures of the ductile-brittle transitions,9 but it was shifted toward still higher temperatures. Longson calculated an activation energy of 2.980 * 0.300 kcal per mole for the hydrogen embrittlement mechanism, compared with 3.180 * 0.400 kcal per mole for hydride formation. Despite this agreement, he concluded, "It seems unlikely that embrittlement results from hydride formation..." because hydrogen embrittlement was observed at temperatures above the solvus. It is our contention that embrittlement is correlated with precipitation of the hydride.6 Because only Longson has investigated Nb-H phase relations at sub-ambient temperatures, we deemed it advisable to re-determine the temperature dependence of the solubility using the resistometric technique already proven successful for the V-H system.6 Coincidence of our solvus with temperatures for embrittlement would

Jan 1, 1970

By W. C. Winegard, W. J. Bratina

Internal friction characteristics and temperature dependence of the torsion modulus for iodide zirconium containing 2.4 pct Hf were investigated, using a low frequency pendulum technique. The internal friction curve consists of a background which increases as the temperature increases, a maximum at 860°C apparently a background due to the al-lotropic transformation, a maximum due to grain boundary relaxation with an associated heat of activation of 58,000 cal per mol, and an anomaly below 350°C which may be associated with a precipitation perphenomenon, Oxygen in below small amounts reduces the grain boundary maximum substantially. The variation of the torsion modulus at 20°C was found to be 3450 Kg per mm2 for the zirconium used in the present work. IT is well known that small amounts of certain solutes materially affect the ductility of zirconium. Lely and Hamburger,&apos; as early as 1914, found that high purity zirconium exhibited a remarkable ductility, while Fast&apos; has shown that oxygen and nitrogen can cause substantia1 embrittlement. Treco" has recently demonstrated that the ductility decreases sharply with the oxygen content, and that 2 atomic pct O2 embrittles zirconium to such an extent that cold working is impossible. The marked decrease in ductility is difficult to understand in view of the fact that Domagala and McPherson4 report the solid solubility of oxygen in zirconium to be 29 atomic pct at 500 °C. Another metal which behaves much the same as zirconium in this respect is titanium. Pratt et al." investigated the internal friction characteristics of titanium and the effect of oxygen on the internal friction values. It is evident that internal friction measurements are of value for studying grain boundary segregation, as shown by Pratt et al. for oxygen in titanium, by Pearson for oxygen in copper, and by Maringer and Schwope for oxygen in molybdenum. With this in view, the internal friction characteristics of zirconium and the qualitative effect of oxygen on the grain boundary relaxation phenomenon were investigated. Materials and Experimental Procedure The zirconium used in the present work was supplied by the Foote Mineral Co. in the form of wire 0.05 in. diam. The analysis supplied by the manufacturer indicates the amount of hafnium as 2.4 pct, less than 0.01 pct O less than 0.01 pct N,, less than 0.02 pct H,, and less than 0.001 pct C. Additional spectro-graphic analysis indicates the other main impurities as follows: 0.01 pct Fe, 0.05 pct Si, 0.008 pct Cu, <0.005 pct W, <0.001 pct Al, <0.05 pct Mg, <0.001 pct Ni, <0.02 pct Ca, and <0.01 pct Ti. Microscopic examination of the material in the as received condition revealed very fine grains with numerous twins. Specimens were annealed either in situ in the internal friction apparatus or in evacuated silica tubes in an auxiliary furnace. When the specimens were annealed in the auxiliary furnace, they were wrapped in identical zirconium wire to prevent contamination by the container. Metallographic sections were taken in all cases. Some were taken from the specimens used for internal friction measurements after completion of the experiments, while others were taken from control specimens at intermediate stages of the experiments. lnternal friction values were obtained by measuring the free decay of a low frequency torsion pendulum (1 cycle per sec), the suspension of which was

Jan 1, 1957