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By S. N. Singh, M. C. Flemings

Results are presented of a detailed study on the combined influences of ingot dendrite am spacing and thermomechanical treatments on the structure and solution kinetics of high --purity cast and worked 7075 alloy. Solution kinetics were found to depend sensitively on ingot dendrite am spacing and on details of therrnomechanical processing, including amount of reduction and extent of&apos; solution treatment before reduction. An approximate analysis is given for rate of solution of nonequilibrium second phase in the cast and worked structres; results of the analysis are compared with experiment. MICROSEGREGATION in high strength aluminum alloys manifests itself as "coring" (composition differences within the primary aluminum-rich phase), and as interdendritic second phase. The mechanism of formation of the microsegregation is understood, and approximate prediction of the amount of second phase is possible for simple binary systems.1,2 When alloy elements or impurities are present in amounts less than their solid solubility at solution temperature, any phases forming from these elements are termed "nonequilibrium" and can be dissolved by appropriate solution treatment. The rate at which the nonequilibrium phases are removed depends sensitively on their spacing (dendrite arm spacing in the cast material, or band spacing in wrought material). When alloy elements or impurities are present in amounts in excess of their solubility at the solution temperature, second phase particles form an "equilibrium" second phase that does not dissolve in heat treatment and may, in fact, coarsen in such treatment. Usual commercial, high strength, wrought aluminum alloys contain nonequilibrium second phases that were not fully dissolved during ingot processing. They also contain equilibrium second phases resulting from impurities present in amounts greater than their solubility. As has been shown by Antes, Lipson, and Rosenthal,3 and will be demonstrated further in a subsequent paper by the authors,4 significant improvements in mechanical properties of high strength alloys can be achieved by reduction or elimination of these second phases. Methods of elimination are 1) to employ high purity materials to minimize amounts of equilibrium second phase, and 2) to employ suitable thermomechanical processing techniques to fully eliminate nonequilibrium second phases. Work reported herein comprises a study of selected thermomechani- cal processing treatments, and of their influence on solution kinetics of wrought high purity 7075 alloy. EXPERIMENTAL PROCEDURE Melting and Casting. The bulk of the work reported was performed on a single ingot of high purity 7075 alloy. The ingot was 4 in. by 4 in. by 8 in. high, uni-directionally solidified following a procedure previously described.5 The mold was heated to 1350°F before pouring the melt. The bottom chill was carbon coated stainless steel. Water was circulated through the chill after the melt was poured. The 7075 alloy was prepared from high purity virgin material (aluminum, zinc, magnesium) and from master alloys (Al-50 pct Cu, A1-15 pct Cr, A1-5 pct Ti). Final measured melt composition (wt pct) was: Zn Mg Cu Cr Ti Fe Si Al 5.70 2.28 1.35 0.18 0.15 <0.002 <0.012 bal Melting was done in a silicon carbide crucible; all tools were coated with zircon wash to minimize iron contamination; degassing was by bubbling chlorine through the melt. che-rmomechanical Treatments. Detailed studies were made on material taken from a location approximately 13 in. from the chill and 51/2 in. from the chill (i.e., from 1 in. thick slices taken between 1 and 2 in. from the chill and between 5 and 6 in. from the chill). Solution treatment was done at 860°F in an air-circulating furnace with a "bottom drop" arrangement to achieve minimum delay time between solution treatment and quench. Samples solution treated in this way were 2 in. by 2 in. by 1 in. Temperature of the quench water was approximately 10°C. Mechanical reduction was by cold rolling. Samples 11/2 and 51/2 in. from the chill were treated for 12 and 24 hr, respectively, before cold rolling. Reduction by cold rolling was then 4/1, 16/1, and 35/1. In each case, several intermediate anneals (1/2 hr at 860°F) were used to permit reaching the final thickness without cracking; two such anneals were used for the 4/1 reduction, five for 16/1, and six for 35/1. After working, materials were again solution treated for various lengths of time from 0 to 48 hr and quenched in water. Structural Measurements. Secondary dendrite arm spacings were measured using procedures previously described.&apos; For each measurement reported, five photomicrographs were first made at X75. Measurements were made of dendrite arm spacings in at least 20 different grains (grain structure was equiaxed). Grain size measurements were made by running a number of random traverses across photomicrographs of the samples and obtaining the mean lineal intercept. Measurement of the volume percent of second phase and porosity was done by quantitative metallography. A two-dimensional systematic point count was used

Jan 1, 1970

By M. V. Nevitt

In the systems Ti-Mn-O, Ti-Fe-O, Ti-Co-O, and Ti-Ni-O the bounda.r-ies of the Ti2Ni-type phases were determined at one or more temperatures and the variation of the lattice parameter with oxygen content was determined. Densities were calculated from the lattice parameters and compared with measured density values. The: results indicate that the occurrence of the phase in these systesms can be correlated qualitatively with valency electron concentration, and that the role of oxygen is that of an electron acceptor. The lower limit of oxygen solubility appears to be determined by the valencies of Mn, Fe, Co, and Ni, while the maximum oxygen concentration coincides with the filling of the 16 (c) positions of the O 7h - Fd 3m space group. THE suggestion has been made by several investigators&apos;" that the phases having the cubic E9,-type structure, and known as 17-carbide-type, double-carbide-type and Ti,Ni-type, are members of a family of electron compounds. This concept has been given additional support by recent work8 in which new isostructural phases involving second and third long period combinations were found, and which provided further evidence of the regularity of occurrence of the phase in terms of periodic table relationships. In this laboratory attention has been focused on the isomorphs containing titanium, zirconium, or hafnium, and the role that oxygen plays in their occurrence. In some binary systems Ti,Nitype* phases occur having the formula A,B where A is the titanium group element. Based on previous workq and the present investigation, oxygen is known to be soluble in two of these binary phases, Ti,Co and Ti2Ni. It is probable that oxygen is also soluble in the other phases of this kind. In other binary systems the Ti,Ni-type phase does not occur, but does occur in the corresponding ternary systems with oxygen .3-5 The experiments described here were performed to determine whether the occurrence and composition of certain of the Ti,Ni-type phases could be related to an electronic effect and whether oxygen&apos;s stabilizing role is exerted through an influence on the electron: atom ratio. The ternary systems Ti-Mn-O, Ti-Fe-O, n-Co-O, and Ti-Ni-O were selected for study for two reasons: First, several schemes have been proposed for first long period elements which, although not in quantitative agreement, show a generally consistent trend for the variation of valency with atomic number. Although for a transition metal the term valency is difficult to define and is generally not a constant number which can be applied to all alloys, it is usually assumed to be an index of the number of electrons per atom involved in metallic cohesion. Second, the determination of the Ti2Ni-type phase boundaries was facilitated by the fact that the phase relations in several of these ternary systems have been investigated by other workers."&apos; EXPERIMENTAL PROCEDURE___________________ The alloys were prepared by arc melting crystal-bar titanium, reagent grade TiO, and electrolytic manganese, iron, cobalt, and nickel. Each button was remelted at least three times. The metals had a minimum purity of 99.9 pct except the nickel whose purity was 99.4 pct, the major impurity in this instance being cobalt. The preparation of the manganese alloys was attended by the customary difficulties associated with the vaporization of manganese. The technique used in this case was to add approximately 10 pct extra manganese to the original charge and to continue remelting the button until the final weight was in agreement with its intended weight. At least three alloys in each system were analyzed chemically and the results, even for the manganese alloys, were in good agreement with the intended compositions. A few additional alloys in the Ti-Mn-O system were prepared by the sintering of mixed powders in evacuated quartz tubes followed in some cases by arc melting. For annealing, the alloys were wrapped in molybdenum foil and placed in fused silica tubes containing zirconium chips. The fused silica tubes were evacuated at room temperature to a pressure of 1 x l0-6 mm of Hg and sealed. These capsules were then annealed for 72 hr at an external pressure of 5 x 10-5 mm of Hg in a vacuum furnace whose temperature could be controlled to + 1°C. The success of this procedure in avoiding significant oxygen or nitrogen pickup was indicated by the bright, ductile condition of the molybdenum foil and by the complete absence of a microscopic reaction layer on the specimens. This method did not permit rapid quenching of the specimens but in no case did metal-lographic examination indicate that a solid-state transformation had occurred on cooling. Metallo-

Jan 1, 1961

By Rudolph G. Wuerker

Charles T. Holland (Head, Dept. of Mining Engineeri*, Virginia Polytechnical Inst., Blacksburg, Va.) Mr. Wuerker has presented a very interesting discussion of the use of triaxial test methods for investigating the strength properties of rocks. Such methods, no doubt, eventually will develop considerable information of interest to those concerned with the design of mine layouts, particularly in the field of pillar design. From his discussion of my recent article, "Cause and Occurrence of Coal Mine Bumps" (Holland Mining Engineering 1958, p. 933-1002), it is evident that in one place at least I did not make my meaning clear to him and perhaps others. To clear the matter up I think it best to quote from the article, somewhat more fully than did Mr. Wuerker, as follows: "4) In actual operations — because rocksare not perfectly elastic, homogeneous, nor isotropic and because local yield does occur — the maximum stress as demonstrated by Phillips (Ref. 22, pp. 64, 65) and indicated by much experience in mining, does not occur at the walls of the opening but at a short distance inside the pillar. Furthermore, the maximum stress does not reach as great a value as theoretical considerations and laboratory experimental methods indicate.* Actual distance inside the pillar, measured from the wall, at which the maximum stress exists, has not been determined. Observations in many mines, however, indicate that this distance could have a mini-value of one to six or eight times the bed thickness and that it is probably affected by width and height of the opening, depth of cover, and relative values of the elasticity and plasticity of materials comprising the roof, floor, and coal seam. The actual value of the stress produced probably lies between the theoretical maximum and the average stress concentration that would be produced if the weight of the strata above the unsupported opening were evenly distributed over the pillars for a distance equal to the opening width." The footnote reference in the above quotation referred to the following: "*For example, the Pocahontas No. 4 coal bed in southern West Virginia is mined under cover up to 1800 ft thick. Development openings are driven 18 to 20 ft wide, and the bed is about 6 ft thick. According to the work of Panek, the tangential wall stress at mid-bed height under these conditions would reach values between 4000 and 5000 psi. Actual tests of 3-in. cubes of this coal show its compressive strength would be much less than this, perhaps as low as 400 psi. Yet the pillars usually show no evidence of failure in these headings. In this same bed at a depth of 800 ft, the author has seen an opening 225 ft between supports lying between two old groves approximately 1100 ft apart. According to the theoretical considerations, the stress in the pillar walls would have been about 18,000 psi, yet the pillar showed little or no evidence of weight. In view of these observations, it is clear that the wall stress does not attain the maximum values indicated by theory." (Underlining added to original wording.) By referring to Fig. 2A of my paper it will be noted that theoretically the maximum pillar stress would occur at the pillar wall, i.e., at the passageway surface of the pillar. Obviously this cannot be correct in the cases of stress ranging from 4000 to 18000 psi since the coal at the surface of the pillar is under no constraint and cannot have a strength much greater than 400 or 500 psi. Hence, my conclusion that the maximum stress does not occur at the wall but back in the pillar some distance from the wall. Since these stresses are pushed back in the pillar from the wall, it is also obvious that the loads transferred to the pillar from the opening will be spread over a greater area and hence Pillar stresses will not rise to the values postulated by theory and photoelastic experiment. Further since to visual inspection the coal along the pillar wall did not appear to be failed the conclusion was reached that the stress shift was caused by local elastic or plastic yield and by difference in the elastic modulus of the rocks composing the mine floor, mine roof, and coal bed. Later on under the heading "Strength of Mine Pillars" (pages 1000-1002) the effects of constraint is briefly described. Also a formula taking into account constraint is developed relating pillar strength to the uniaxial strength of coal and the L/T ratio of the pillar. Since my paper was written, reports of experiments conducted in South Africa (Denkhaus, et. al., 1959), in Sweden (Hast 19581, and in Canada (McInnes, et.al., 1959) reveal that the conclusion expressed relative to the existence of a low stress area existing around the edges of pillars and solid faces as described above is generally correct. But it seems possible that where the wall stress developed is less than the unconfined strength of the rock composing the pillar and where the roof, floor, and pillar

Jan 1, 1961

By Jaakko Kajamaa

Neutron diffraction was applied to determine sheet textures by the transmission method. Cold-rolled and recrystallized copper sheets were investigated. The amount of cube texture was determined for three compositions, in which the phosphorus content was, respectively, 0, 0.005, and 0.03 wt pct. The heat treatment was in every case 8 sec at 650°C. In the two latter cases the cube texture was prevented. In addition a comparison with the X-ray diffraction transmission method was made with the 96 pct cold-rolled copper sheet. Outer parts of both (111) pole figures can be considered to be rather identical. This is seen from the fact that the intensity ratio ITD/120" was 0.45 for neutron diffraction and 0.40 for X-ray diffraction. Differences between the methods were discussed in detail. Features peculiar to neutron and X-ray diffraction in texture studies were listed and compared. In this work neutron diffraction was applied to determine sheet textures. Specifically, it was desired to ascertain whether this method can be used to reveal differences when compared to other methods. In addition, the amount of the cube texture in copper sheets was determined as a function of phosphorus content. Previous applications of neutron diffraction to texture problems include the following: nickel wires,&apos; wire of some bcc metals,&apos; and uranium bars.3 In the neutron diffraction technique the greatest difference is in the sample—its method of production and its volume. A sample needs no treatment and its volume is roughly 105 times larger than the volume of an X-ray diffraction sample. The cold-rolled sheet was investigated both by neutron diffraction and by X-ray diffraction, because it is expected that, due to large number of defects, possible differences in the results of the two methods would be revealed. It is a well-known fact that X-ray lines show broadening when cold-worked. Analysis has shown that this is based chiefly on small crystalline size, micro-stresses, and/or faults.4&apos;5 Neutrons are sensitive to the above-mentioned disturbing factors as well, but circumstances in diffraction are different from the X-ray case. Because the sample represents a larger volume, the result is an average over that volume. In addition, it can be assumed that the sample has preserved its original structure, because it needs no special preparation. The particular limitation of neutrons is the relatively low neutron intensity available from nuclear reactors. This decreases the resolution as compared to the X-ray diffraction methods. Furthermore, absorption mainly reduces diffracted X-ray intensity, while multiple scattering effects, i.e., secondary extinction, disturb neutron diffraction. SO neutrons and X-rays behave in a different way when interacting with matter. As in other structural investigations, one can utilize this difference in texture studies as well. One cold-rolled and three recrystallization textures in copper sheets were investigated by neutron diffraction. The samples were produced at the Outokumpu copper factory to the specifications shown in Table I. The paper is divided into five parts. The first deals with the theory of the measurement. In the second, experimental procedures are described. Results are presented in the third part. Both cold-rolled and re-crystallized samples are studied. Discussion is in the fourth part, and finally in the fifth part some conclusions are drawn. 1) THEORETICAL CONSIDERATIONS Properties peculiar to neutron diffraction are the following: a) the scattering length varies greatly between one element and another; b) many of the elements do not absorb neutrons appreciably. In this connection it is of primary interest to know the interaction of neutrons with lattice imperfections. As with X-rays this problem leads to diffraction analysis of deformed and recrystallized metals. From the physical point of view the main difference is that neutrons are scattered by nuclei (magnetic scattering is not considered here), whereas X-rays are scattered by electrons. The features peculiar to neutron and X-ray diffraction methods in texture studies are listed in Table 11. Pole figures are an important tool in performing structural analysis of deformed or recrystallized metal. Present texture research technology requires pole figures which are as precise as possible. The choice between these two methods depends on the technical information which is required. The X-ray diffraction transmission technique may give results which are not necessarily representative of the average physical state of the sample. Although foil samples normally contain enough crystallites for diffraction, they may not necessarily represent the whole structure. An example of this problem is the frequently observed difference between the "surface" and the "inside" texture of a sample. The production of foil samples may disturb the original structure of the parent material. The selection and orientation of the foil from the sample is quite arbitrary. Normally, a highly deformed piece of metal has several texture components. Different components are deformed in a slightly different manner. This is a re-

Jan 1, 1969

By Martin F. Littmann

Inclusions of MnS and Fe3C have been introduced into single crystals of 3 pct Si-Fe to study their effects on recrystallization behavior and textures after cold rolling and annealing. The presence of MnS in (110) [001] and (111)[112] crystals inhibited primary grain growth and promoted secondary recrystallization but did not alter the texture significantly after annealing at 1200°C. The presence of Fe3C in (llO)[OOl] and (100)[001] crystals caused a refinement of the primary re crystallized grain size but did not promote secondary recrystallization. THE texture behavior of single crystals of 3 pct Si-Fe during deformation and recrystallization has been studied by numerous investigators. The early work of Dunn&apos; followed by Decker and Harker2 involved relatively small cold reductions. More detailed studies of Dunn3&apos;4 and of Dunn and Koh5&apos;6 involved a reduction of 70 pct and recrystallization at 980°C for several crystals. Walter and Hibbard7 studied a greater variety of initial orientations and sought to relate the textures to those of polycrystalline material. Attention was focused on the nucleation process during early stages of annealing and on surface energy effects in studies by Walter and Dunn8 and by HU.9&apos;10 One of the most extensive investigations has been reported by T. Taoka, E. Furubayashi, and S. Takeuchi.11 Most of this work has been conducted using relatively pure crystals with minimal amounts of precipi-tate-forming elements such as carbon, oxygen, sulfur, and nitrogen. Recently, however, S. Taguchi and A. Sakakura have observed that AIN precipitates can alter the recrystallization textures of rolled (100)[001] crystals.12 The present studies were initiated to determine effects of MnS and Fe3C precipitates on recrystalli-zation and grain growth behavior of rolled single-crystals of 3 pct Si-Fe. Both of these types of inclusions play significant roles in the recrystallization behavior leading to the formation of the (110)[001] or cube-on-edge texture in commercial grain-oriented silicon iron. It is well known that (110)[001] primary grains are formed by recrystallization of (110)[001] or (11 l)[ 112] crystals after cold reduction of about 60 pct or more. Crystals of these orientations, therefore, were selected for study of the effect of MnS in-clusions on grain growth. On the other hand, a major component of the texture of cold-rolled, polycrystal-line 3 pct Si-Fe is the (100)[011] orientation. The function of Fe3,C inclusions is of interest for this orientation. EXPERIMENTAL PROCEDURE The single crystals used are listed in Table I and were obtained from commercial Si-Fe alloy processed to produce (110)[001] and (100)[001] texture by secondary growth. The cube-on-edge material was 0.59 mm thick. Suitably large (110)[001] crystals 25 mm wide were selected and their orientations were determined using an optical goniometer. Etch pits for texture determination were formed by a ferric sulfate solution. The other crystals used in the study with (100)[001], (100)[011], and (111)[112] orientations were obtained from sheet which contained large grains developed from secondary recrystallization by a surface-energy driving force.13 Most crystals had a (100) plane very nearly parallel to the sheet surface and the rolling direction could be selected readily. The same sheet also contained a few crystals with (111) planes parallel to the sheet surface, these also being a result of growth by surface energy. The crystals selected from the sheet were about 25 mm wide and 0.25 to 0.28 mm thick. As shown in Table 11, the crystals already contained about 0.070 to 0.10 pct Mn. Inclusions of MnS were incorporated into crystal 36 in the following manner. The crystals were first sulfurized by holding them Table I. Initial Orientations of Crystals Crystal No. Initial Orientation Thickness, mm Special Treatment 34 (I10) [00l]* 0.59 None 36s (110) [001] 0.59 Sulfide precipitates added 30,40 (111)[Ti21 0.28 None 43s (III) [Ti21 0.28 Sulfide precipitates added 37 (100) [Oll] 0.30 None 37C (100) [01I] 0.27 Carbon added 41 (100) (01I] 0.25 None 41C (100) [OI11 025 Carbide precipitates added 42 (100) [OOl] 0.25 None 42C (100) [001] 0.25 Carbide precipitates added *Tilted 4 deg to r~ght about R.D. Table II. Compositions of Crystals Special Treatments Base Analysis ~ ______________________£________________Crys- Crystals Pct Si Pct C Pct Mn Pct S Pct N Pct Al tal Pct C Pct S 34.36 2.93 • 0.099 <0.005 - 0.0014 36S 0.011 30.37 to 42 2.78 0.0057 0.070 0.001 0.0008 0.0011 43S 0.022 37C 0.029 -41C 0.028 -42C 0.026 *Estimate 0.004 pct. Oxygen estimated <0.003 pct on all samples

Jan 1, 1970

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.&apos; Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.&apos;&apos; As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

By O. D. Gaither

This paper is an analytical study of the flow of fluids through small vertical conduits. Small conduits are defined as 11/4-in. nominal diameter tubing size and smaller, and approximately twice this area for annular conduits (i.e., 1- X 21/2-in. annulus and smaller). Experimental data are presented for the 1-X2-in. and 11/4- X 2%-in. annuli, and the I-in. and 11/4-in. tubing, since these represent the small conduit sizes and configurations generally encountered in oilfield applications. Data have been gathered for these conduits for single-phase water, single-phase gas and two-phase water-gas mixtures, with particular emphasis on high gas-liquid ratios. Water rates in excess of 2,000 BID and gas rates in excess of 2.5 MMcf/D, and two-phase flow ratios in between these two, represent the scope of the data gathered. Existing equations have been applied to predict flowing pressures and compared with experimental data. New correlations have been developed. INTRODUCTION The increased economic pressure on the domestic oil industry in the United States has constantly required the use of new techniques and equipment designed to reduce the cost of finding and producing oil and gas. Since tangible items are most readily apparent in economic analysis, the advent of lower-cost well completions was inevitable. One of the methods used to reduce costs which has received widespread attention is the slim-hole completion technique where tubing is used as the well casing and in which small conduits are used for tubing if necessary. Small conduits, defined by Kirkpatrick1 as "11/4-in. diameter nominal tubing and smaller for tubing flow and less than twice the 11/4-in. diameter nominal tubing internal flow area for annulus flow", have also found widespread usage as siphon strings for de-watering gas wells and as "kill" strings in deep high-pressure oil and gas wells. The growing use of small-diameter tubing has resulted in an increased need for development of improved methods to measure or predict flowing bottom-hole pressures since the physical dimensions generally preclude the use of subsurface-recording pressure gauges. Even in the cases where small bombs are available, the relatively high velocities encountered at nominal flow rates make it necessary to use excessive weight bars or special hold-down devices. Attempts to use recognized correlations to accurately predict flowing or gas-lift performance in wells equipped with small conduits have been generally unsuccessful. Insufficient field data were available to allow the development of a correlation on this basis, and an experimental approach was applied in an attempt to obtain a workable relation. The experimental approach used to obtain the data presented in this paper was actually a compromise between a field installation and a laboratory study. A test well 1,000 ft in length was used to obtain flow data on single-phase liquid, single-phase gas and two-phase water-gas flowing mixtures. Liquid rates up to 2,200 B/D and gas rates up to 3 MMcf/D were used in the single-phase flow studies. Two-phase flow rates from 100 to 600 B/D with gas-liquid ratios from 500 to 8,000 cu ft/bbl were recorded. Experimental data were obtained for single- and two-phase flow through 1-in and 11/4-in. nominal tubing, and through the annuli between 1- and 2-in. and 11/4- and 2%-in. nominal tubing strings. Experimental results for the two-phase flow are compared to the Poettmann-Carpenter correlation2 which is widely used as a comparative standard for development of multiphase flow predictions in flowing and gas-lift wells. Correlations developed by Tek,3 Baxendell and Thomas" were also investigated. The experimental data recorded herein fell in between the two flow regimes as defined by Ros," and this correlation also failed to yield satisfactory results. The fact that existing correlations failed to confirm the experimental data led to the need for development of a new correlation. Although a two-phase flow study was the primary objective of this investigation, data were also recorded for single-phase flow of water and gas, and constants were developed relating to pipe roughness and equivalent diameters for annular flow. These single-phase studies assisted materially in the development of certain of the two-phase flow results. Considerable previous work has been published which presented relationship of surface measurements to bottom-hole condition. The works of Buthod and Whiteley,6 Jones,&apos; Poettmannb and the Texas Railroad Commission" are classic examples of the successful use of mathematical relationships which allow acceptable predictions of subsurface pressures, when gas is the flowing fluid. Darcy and others have derived relationships which may be used with minor modifications to predict subsurface flowing conditions in injection and water-supply wells. As previously stated, the application of the single-phase flow relationships

By Elmer R. Kaiser

COMBUSTION of coal and transfer of heat from flames and gases to boiler surfaces continue to be of great interest to engineers here and abroad. Numerous investigations have been in progress to improve furnace and boiler performance and economy. The importance of better understanding of the processes and opportunities for improvement is apparent when it is remembered that heat from at least 500 million tons of coal a year the world over is being transferred to boiler water at efficiencies ranging mostly between 50 and 90 pct. Even slight gains in efficiency, economy, and labor saving become very significant when multiplied by the enormous quantity of fuel consumed. Also the competitive position of the large coal, oil, and gas industries in satisfying the fuel consumers is greatly affected by the achievements made through technical progress with each fuel. This paper is part of a continuing activity of Bituminous Coal Research, Inc., to extend the knowledge of coal utilization for steam generation and to seek promising directions for future research and development in cooperation with others. Particularly in the latter regard, numerous interviews were held during the last three years to seek the experience and advice of boiler and combustion-equipment manufacturers, electric-utility executives, and fuel engineers. A wealth of published information was also reviewed, which together with the interviews pointed to the advisability of further work on ash and sulphur control. For the present purpose a number of factors important to efficient heat liberation and recovery have been grouped as follows: 1—combustion, temperatures, and rates of heat liberation; 2—radiation, convection, and furnace and boiler configuration; 3—sponge ash, slag, and hard-bonded deposits; 4— low-temperature deposits and corrosion (cooling flue gas below dew point and air-pollution control); 5—the limitations of coal cleaning and boiler size and cost as related to fuel characteristics; 6—future possibilities and conclusions. The development of combustion apparatus for power boilers is progressing at a lively pace. There has been no letup in improvements in design of pulverized-coal-fired boilers, and there is a strong trend at present toward improving dry-bottom units. Spreader stokers with overfire jets and dust collectors as standard equipment are gaining favor. Less than 10 years in commercial use, cyclone burners are going into numerous installations here&apos; and abroad.&apos; Underfeed and traveling-grate stokers have long since been developed for heavy-duty operation, yet new developments in overfire jets and humidification of air blast have improved their performance. A water-cooled vibrating-grate stoker of German origin is being introduced into the United States and Canada." The primary objectives of an ideal coal combustion device are: capacity to burn the variety and sizes of coals likely to be economically available during the life of the unit; capacity to burn the coals automatically for a wide load range and rapid load fluctuations and to burn the coals completely to CO2, H2O, and SO2, which means without smoke and cinders, or carbon in the refuse; capacity to control and discharge all the ash in final granular form without ash adhesion to walls or tubes, and without flue dust; minimum furnace volume; minimum labor and maintenance; low initial and operating cost. Regardless of the method of burning, the gaseous products of coal combustion are N2, CO2, O2, H20, and SO?. By way of illustration, the coal analyses in Table I is assumed from an installation described by E. McCarthy.&apos; When coal is burned with 20 pct excess air (theoretical air, 9.23 lb per lb of coal), the quantities of combustion gas shown in Table II are produced. In addition, the gases carry particles of fly ash, unconsumed cinders, soot particles, and small but significant amounts of vaporized oxides and sulphates of sodium, potassium, lithium, phosghorous, iron, and other metals. In recent years, germanium, one of the rare metals found in coal, has been shown to oxidize and vaporize at combustion temperatures and to be concentrated by reconden-sation at lower temperatures." Pulverized coal and cyclone flames" have peak temperatures of 3000&apos; to 3500°F. Temperatures in fuel beds of large underfeed stokers reach maxima of 3000°F, sufficient to fuse almost any ash and to volatilize some of it. These peak temperatures are above the optimum necessary for rapid combustion, but they hasten heat transfer for ignition as well as boiler heat absorption. Furnace and gas temperatures increase with combustion air preheat. Low excess air has the same effect. Fine coal pulverization and highly turbulent combustion shorten the distance for fuel burnout, increase flame temperature, and speed up heat transfer. Rates of combustion of pulverized coal exceeding 200,000 Btu per cu ft per hr have been demonstrated in atmospheric gas-turbine combusters,

Jan 1, 1955

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

By R. A. Flinn, R. D. Pehlke, D. R. Glass, P. O. Hays

Knowledge of the depth of penetralion of an oxygen jet into the bath of the oxygen converter and of the correlation of penetration with driuing pressuve, lance heighl, and nozzle throat area is vital to the understanding of converter operation. If the penetration is too shallow, then severe and hazardous slopping takes place. On the other hand, if the jel penetrates entirely Lhvough lhe bath for an apprcciublc period of time, bottom damage occurs. In addilion to measurement of the penetralion of the jel, knou~ledge of the circulatory movement in the bath is also of interest in order to evaluale various theories oj-concerter operating behavior which have been published. In this investigation, experimental converters were buill of IOU- , 300-, and 4000-lb capacity. Four independent methods were used to determine penelralion: the onset of bottom marking, a nitrogen bubbler probe, observation througlt an optical syslew built into the oxygen lance, and direcl viewing of the jet issuing from the bottom of the vessel. Good correlation zuas obtained, and empirical relalions for pvedicling perletration were found. These relations were conjzrmed by bottom marking tests in 55- and 110-ton vessels. Within the operaling conditions employed in these tests, the depth to which a single oxygen jet penetrated zuas found lo vary according to the relatiorl ThE technical literature is replete with data concerning the successful use of the basic oxygen furnace or converter in steelmaking. Experimental data are lacking, however, on the vital factors of the depth of penetration of the jet into the bath and the induced circulation. Commercial operating conditions usually have been the result of cut and try experiments in lance manipulation until satisfactory results were obtained. There have been, however, two hotly argued opposing theories concerning desirable depth of penetration and these are exemplified by the Schwarz and Miles patents1,2 on one hand and the Suess patent3 on the other. The Schwarz patent teaches that the jet, issuing from the nozzle at supersonic speed, penetrates deeply "so that the reactions between the iron and the oxygen and between the oxygen and the rest of the smelting components take place in the center of the bath". Specific operating suggestions are given by Miles.2 By contrast, the Suess patent calls for surface Circulalion was investigated by lour methods: by direct observation in 200-lb open baths, by the use of graphite rudders in the 300- and 4000-lb converlers, by direct observalion through an oplical system in the lance, and by various models al room temperature. All were in excellent agreement and indicated that the motion of the bath ulas up at the center, radially outluavd at the surface, and down at the sides. Experi-ments in small and in commercial vessels indicate that it is essential to operate with a jet penetration of approximately 50 pct of the bath depth. Surface blowing results in low oxygen eficienty and in hazardous conditions which may render the process inopeuable. RejYactory dartzage al the bottom of the vessel is only encountered when the jet penetrates to the bottom, and this can be avoided by properly applying the penetration formula. The application of this en/pirical formula in commercial peraations is best when limited to combinations of lance size, pressure, and height which are typically encounteved in the use of a single-hole lance. blowing so that "...the oxygen jet does not penetrate deeply into the molten metal bath and is confined to an impingement area at the central portion of the bath surface". These references are given merely to illustrate the basic differences between the two schools of thought and to point out the need for measurement of penetration for the sake of the operator. For example, it is shown later that inefficient and even dangerous conditions can arise if improper blowing conditions are used. Differences are also evident between the two schools of thought as to the mixing, circulation, and agitation which is to be accomplished by the jet. The Schwarz patent states that "surface contact is not sufficient in most cases to bring about quick reaction, the same as the blowing of the gas over the bath surface or the mere blowing of the gas onto the bath surface". The patent goes on to call for active mixing. In contrast the claims of the Suess patent call for "discharging a stream of oxygen ... to an extent to avoid material agitation of the bath by the oxygen stream". In this patent the circulation is said to be downward in the center and up at the sides of the vessel. A number of investigators4-12 have explored penetration and circulation in transparent models. In general, it is agreed in these tests that the circulation is upward at the center (along the sides of the jet cavity),

Jan 1, 1968

By J. B. Clark

The oil industry has long recognized the need for increasing well productivity. To meet this need, a process is being developed whereby the producing formation permeability is increased by hydraulically fracturing the formation. The "Hydrafrac" process, as it is now being used, consists of two steps: (1) injecting a viscous liquid containing a granular material, such as sand for a propping agent, under high hydraulic pressure to fracture the formation; (2) causing the viscous liquid to change from a high to a low viscosity so that it may be readily displaced from the formation. To date the process has been used in 32 jobs on 23 wells in 7 fields, resulting in a sustained increase in production in 11 wells. INTRODUCTION Need For Process Although explosives, acidizing, and other methods have long been used, there still exists a need for artificial means of improving the productive ability of oil and gas wells, particularly for wells which produce from formations which do not react readily with acids. This paper discusses the development of a hydraulic fracturing process, "Hydrafrac", which shows distinct promise of increasing production rates from wells producing from any type of formation. The method is also considered applicable to gas and water injection wells, wells used for solution mining of salts and, with some modification, to water wells and sulphur wells. Requirements of Process In considering such a possible process, it appeared that certain requirements must be met. Some of these are as follows: A. The hydraulic fluid selected must be sufficiently viscous that it can be injected into the well at pressure high enough to cause fracturing. B. The hydraulic fluid should carry in suspension a propping agent, such as sand, so that once a fracture is formed, it will be prevented from closing off and the fracture created will remain to serve as a flow channel for oil and gas. C. The fluid should be an oily one rather than a water-base fluid, because the latter would be harmful to many formations. D. After the fracture is made, it is essential that the fracturing fluid be thin enough to flow hack out of the well and not stay in place and plug the crack which it has formed. E. Sufficient pump capacity must be available to inject the fluid faster than it will leak away into the porous rock formation. F. In many instances, formation packers must be used to confine the fracture to the desired level, and to obtain the advantages of multiple fracturing. Development of Process As a necessary step in the development of this process, it was deemed advisable to determine if the Hydrafrac fluids were actually fracturing the formation or whether these special fluids were merely leaking away into the surrounding formation. To determine this, a shallow well, 15 feet deep, was drilled into a hard sandstone. Casing was set, the plug drilled, and the well deepened in the conventional manner. A fracturing fluid dyed a bright red was used to break down the formation. Sand mixed with distinctively colored solids was injected into the well with the fracturing fluid to prop open any fracture made in the formation. A simulated gel breaker solution dyed a bright blue was then pumped into the well to determine if the gel breaker would follow the first solution. The results are shown in Figure 1. It was noted that a fracture was formed about the well bore, that the propping agent was transported back into the break, and that the breaker solution did actually follow the fracturing gel out into the fracture. While it is realized that this shallow well test is probably not exactly equivalent to a deep test, the results were interpreted as being a definite indication of what happens down the hole during a Hydrafrac job. Of interest in this connection is an investigation reported by S. T. Yuster and J. C. Calhoun, Jr.&apos; This study, re~orted after the Hydrafrac work was under way, presents some excellent field data supporting the theory of fracturing a formation with hydraulic pressure. METHOD Steps of Hydrafrcu: Process Figure 2 shows a simplified cross-sectional view of a well treated by one version of the process. The first step, formation breakdown, is done with a viscous fluid, usually consisting of an oil such as crude oil or gasoline, to which has been added a bodying agent. Due to availability and price, war-surplus Napalm has been used in the majority of experiments to date. Napalm is the soap which was used in the war to make "jellied gasoline". The next step consists of breaking down the viscosity of the gel by injecting a gel-breaker solution and then after several hours, putting the well back on production. Figure 3 shows diagram-matically, a typical field hookup. The oil or gasoline is unloaded into the 10 bbl. tank shown on the left rear of the truck. This base fluid is picked up by the mixing pump and pumped through the jet mixer, where the granular soap is added. Next it goes into a small mixing tub, from which the high-pressure pump takes suction. The solution is then pumped into the well. The breaker solution is then taken from an extra tank and is displaced into the well immediately following the gel. When required, additional trucks may

Jan 1, 1949

By J. B. Clark

The oil industry has long recognized the need for increasing well productivity. To meet this need, a process is being developed whereby the producing formation permeability is increased by hydraulically fracturing the formation. The "Hydrafrac" process, as it is now being used, consists of two steps: (1) injecting a viscous liquid containing a granular material, such as sand for a propping agent, under high hydraulic pressure to fracture the formation; (2) causing the viscous liquid to change from a high to a low viscosity so that it may be readily displaced from the formation. To date the process has been used in 32 jobs on 23 wells in 7 fields, resulting in a sustained increase in production in 11 wells. INTRODUCTION Need For Process Although explosives, acidizing, and other methods have long been used, there still exists a need for artificial means of improving the productive ability of oil and gas wells, particularly for wells which produce from formations which do not react readily with acids. This paper discusses the development of a hydraulic fracturing process, "Hydrafrac", which shows distinct promise of increasing production rates from wells producing from any type of formation. The method is also considered applicable to gas and water injection wells, wells used for solution mining of salts and, with some modification, to water wells and sulphur wells. Requirements of Process In considering such a possible process, it appeared that certain requirements must be met. Some of these are as follows: A. The hydraulic fluid selected must be sufficiently viscous that it can be injected into the well at pressure high enough to cause fracturing. B. The hydraulic fluid should carry in suspension a propping agent, such as sand, so that once a fracture is formed, it will be prevented from closing off and the fracture created will remain to serve as a flow channel for oil and gas. C. The fluid should be an oily one rather than a water-base fluid, because the latter would be harmful to many formations. D. After the fracture is made, it is essential that the fracturing fluid be thin enough to flow hack out of the well and not stay in place and plug the crack which it has formed. E. Sufficient pump capacity must be available to inject the fluid faster than it will leak away into the porous rock formation. F. In many instances, formation packers must be used to confine the fracture to the desired level, and to obtain the advantages of multiple fracturing. Development of Process As a necessary step in the development of this process, it was deemed advisable to determine if the Hydrafrac fluids were actually fracturing the formation or whether these special fluids were merely leaking away into the surrounding formation. To determine this, a shallow well, 15 feet deep, was drilled into a hard sandstone. Casing was set, the plug drilled, and the well deepened in the conventional manner. A fracturing fluid dyed a bright red was used to break down the formation. Sand mixed with distinctively colored solids was injected into the well with the fracturing fluid to prop open any fracture made in the formation. A simulated gel breaker solution dyed a bright blue was then pumped into the well to determine if the gel breaker would follow the first solution. The results are shown in Figure 1. It was noted that a fracture was formed about the well bore, that the propping agent was transported back into the break, and that the breaker solution did actually follow the fracturing gel out into the fracture. While it is realized that this shallow well test is probably not exactly equivalent to a deep test, the results were interpreted as being a definite indication of what happens down the hole during a Hydrafrac job. Of interest in this connection is an investigation reported by S. T. Yuster and J. C. Calhoun, Jr.&apos; This study, re~orted after the Hydrafrac work was under way, presents some excellent field data supporting the theory of fracturing a formation with hydraulic pressure. METHOD Steps of Hydrafrcu: Process Figure 2 shows a simplified cross-sectional view of a well treated by one version of the process. The first step, formation breakdown, is done with a viscous fluid, usually consisting of an oil such as crude oil or gasoline, to which has been added a bodying agent. Due to availability and price, war-surplus Napalm has been used in the majority of experiments to date. Napalm is the soap which was used in the war to make "jellied gasoline". The next step consists of breaking down the viscosity of the gel by injecting a gel-breaker solution and then after several hours, putting the well back on production. Figure 3 shows diagram-matically, a typical field hookup. The oil or gasoline is unloaded into the 10 bbl. tank shown on the left rear of the truck. This base fluid is picked up by the mixing pump and pumped through the jet mixer, where the granular soap is added. Next it goes into a small mixing tub, from which the high-pressure pump takes suction. The solution is then pumped into the well. The breaker solution is then taken from an extra tank and is displaced into the well immediately following the gel. When required, additional trucks may

Jan 1, 1949

By C. T. Wei, A. Kelly

USING a recently developed X-ray method, reported by Schulz,2 it is possible to make a rapid survey of the perfection of a single crystal at a particular surface. This technique has the advantage of allowing a large surface of a specimen to be examined by taking a single photograph and it compares well with other X-ray methods in regard to sensitivity of detection of small angle boundaries. During the course of a survey of the perfection of large crystals of aluminum produced by a number of methods, an examination has been made of a number of single crystals produced from the melt using a soft mold (levigated alumina)." Crystals grown by this method are known, from an X-ray study carried out by Noggle and Koehler,3 to contain regions where they are highly perfect. In the present work, it has been possible to obtain photographs showing directly the distribution of low angle boundaries at a particular surface of these crystals. single crystals were grown from the melt using the modified Bridgman method with a speed of furnace travel of -1 mm per min. These were about 1/10 in. thick, 1 in. wide, and several inches long. The metal was 99.99 pct pure aluminum supplied by the Aluminum co. of America. The crystals were examined by placing them at an angle of about 25° to the X-ray beam issuing from a fine focus X-ray tube of the type described by Ehrenberg and Spear4 and constructed by A. Kelly at the University of Illinois. A photographic film was placed SO as to record the X-ray reflection from the lattice planes most nearly parallel to the crystal surface. The size of the focal spot on the X-ray tube was between 25 and 40 u, and the distance from the X-ray tube focus to the specimen (approximately equal to the specimen to film distance) was -15 cm. White X-radiation was used from a tungsten target with not more than 35 kv in order to reduce the penetration of the X-rays into the specimen. Exposure times were approximately 1 hr with tube currents between 150 and 250 microamp. The type of photograph obtained from these crystals is illustrated in Fig. 1, which shows a number of overlapping reflections from the same crystal. The large uniform central reflection is traversed by sets of horizontal white and dark lines. These two sets run mainly parallel to one another. Lines of one color are wavy in nature and often branch and run together. Large areas of the crystal surface show no evidence of these lines whatsoever. The lines are interpreted as being due to low angle boundaries in the crystal, separating regions which are tilted with respect to one another. A white line is formed when the relative tilt forms a ridge at the interface and a black line is found when a valley is formed. In a number of cases, the lines stop and start within the area of the reflection and often run into the reflection from the edge, corresponding to a low angle boundary starting from the edge of the crystal. The prominent lines run roughly parallel to the direction of growth of the crystal although narrow bands can run in a direction perpendicular to this; see Fig. 2. Although they may change their appearance slightly, the lines tend to occur in the slightly,Same place in the X-ray image and to maintain their rough parallelism when the crystals are reduced in thickness by etching. Thus the low angle boundaries can occur at any depth within the crystal. The appearance of the lines is unaffected by subjecting the crystal to rapid temperature changes, such as plunging into liquid nitrogen or rapid quenching from 620°C. From the width of the lines on the x-ray reflection, values can be found for the angular misorienta-tion of the two parts of the crystal on either side of a boundary. The values found run from 1&apos; to 10&apos; of arc, but values of UP to 20&apos; have sometimes been found, e.g., the widest lines on Fig. 2. These mis-orientations are much less than those commonly found in crystals possessing a lineage structure. When a number of a and white lines occur, running in a roughly parallel direction across the image of a Crystal, the total misorientation corresponding to lines of one color is approximately equal to that corresponding to lines of the other color. The interpretation of the lines as due to low angle boundaries has been checked in a number of ways. Photographs taken with different specimen-to-film distances distinguish lines due to low angle boundaries from effects due to surface relief of the specimen. Normal Laue back-reflection photographs, taken with the beam irradiating an area of the surface showing a number of the lines, show white lines running through each Laue spot. Black lines are set to see by this method. X-ray photographs were also taken, using the set-up described by Lam-one et al.5 when the beam straddles regions giving rise to lines in the Schulz pattern, split reflections are observed within the Bragg spot. The misorienta-tions calculated from the separation of these reflections and that found from the widths of the lines on the schulz technique patterns show good agreement. An exposure was made with Lambot technique of an area of the crystal showing no evidence of low angle

Jan 1, 1956

By T. R. A. Davey

IN 1947 the author became interested in the fundamental aspects of the desilverizing of lead by zinc, conducted some experimental work, and searched the technical literature for all available fundamental data. Since then a revival of interest in the subject in Europe resulted in the appearance of quite a number of papers. It became evident that it would be more profitable to collect together and examine thoroughly the results of various workers, than to attempt to duplicate the experimental determinations. There are many inconsistencies in the various publications, and it is opportune to review at this time the present status of knowledge on the Ag-Pb-Zn system. There is also a need for a clear description, in fundamental terms, of the various desilverizing procedures. This paper is presented in four sections: 1—There is an historical review of the origins of the Parkes process, of the results of many attempts to find a satisfactory fundamental explanation for the phenomena, and of the modifications proposed to date. 2—A diagram of the Ag-Pb-Zn system is presented. This is believed to be free of obvious inconsistencies or theoretical impossibilities, although thermodynamic analysis subsequently may reveal errors. 3—The fundamental bases of the various desilverizing procedures, which have been used up to the present day, are described; and a new method is suggested for desilverizing a continuous flow of softened bullion in which the bullion is stirred at a low temperature in two stages producing desilverized lead at least as low in silver as that from the Williams continuous process and a crust which, on liquation, yields a very high-silver Ag-Zn alloy. 4—A suggestion is made for the revival of de-golding practice, following a recently published account which does not seem to have attracted the attention it deserves. The terms "eutectic trough" and "peritectic fold" as used in this paper are synonymous with "line of binary eutectic crystallization" and "line of binary peritectic crystallization" as used by Masing.&apos; The German literature on ternary and higher systems is rather extensive and a fairly general system of nomenclature has arisen, whereas in English usage the corresponding terms are not as well established. For this reason the meanings of terms used in this paper, together with the equivalent German terms, are given as follows: 1—Eutectic trough—eutektische rinne: line at which a liquid precipitates two solids S1 and S2 simultaneously. If the composition of a liquid which is cooling reaches this line, it then follows the course of this line until a eutectic point is reached, or until all the liquid is exhausted. The tangent to the eutec-tic trough cuts the line joining S1S2. 2—Peritectic fold—peritektische rinne: line at which a solid S1 and a liquid L transform into another solid S2. If the composition of a liquid which is precipitating S1 reaches the line, on further cooling only S2 is precipitated. The liquid composition moves from one phase region (L + S1) into the other (L + S2), and does not follow the course of the boundary. The tangent to the peritectic fold cuts the line S1S2 produced nearer S,. 3—Liquid miscibility gap, or conjugate solution region—mischungslucke: the region within which two liquid phases coexist in equilibrium over a certain range of temperature. A system whose composition is represented by a point in this region comprises one liquid at high temperature; then as the temperature is progressively reduced, two liquids, one liquid and one solid, one liquid and two solids, and finally three solids. 4—Liquid miscibility gap boundary—begrenzung der flussigen mischungsliicke: the line along which the surface of the miscibility gap dome, considered as a solid model, intersects the surrounding liquidus surfaces. 5—Tie lines—konoden: lines joining points representing the compositions of two liquids, a liquid and a solid, or two solids, in equilibrium. In binary systems the only tie lines customarily drawn are those through invariant points, e.g., through the eutectics of the Pb-Zn and Ag-Pb systems, or the various peritectics of the Ag-Zn system, as in Figs. 1 to 3. In ternary systems it is desirable to draw sufficient tie lines to indicate the slopes of all possible tie lines. 6—Ternary eutectic point—ternares eutektikum: point at which liquid transforms isothermally to three solids, S1, S2, and S Such a point can lie only within the triangle 7—Invariant peritectic (transformation) point— nonvariante peritektische umsetzungspunkt: (a) — On the miscibility gap boundary, the point at which two liquids and two solids react isothermally so that L, + S, + L, + S2. (b)—On the eutectic trough, the point at which a liquid and three solids react iso-thermally so that L + S, + S2 + S3. Such a point must lie on that side of the line joining S,S which is further from S,. (c)—A further possibility, not found in this ternary system, is that the point is at the intersection of two peritectic folds when the reaction concerned is L + S, + S, + S Historical Introduction Karsten discovered in 1842 that silver and gold may be separated from lead by the addition of zinc.2 Ten years later Parkes used this fact to develop the well known desilverizing process which bears his

Jan 1, 1955

By A. Y. Bethune, W. G. Woolf

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process&apos; for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt&apos;s earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.&apos;s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By W. G. Woolf, A. Y. Bethune

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process&apos; for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt&apos;s earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.&apos;s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By K. A. Jackson, J. D. Hunt

A general theory for the growth of lamellar and rod eutectics is presented. These modes of growth depend on the interplay between the diffusion required for phase separation and the formation of interphase boundaries. The present analysis of these factors provides a justification for earlier approximate theovies. The conditions for stability of rod and Lanlellar structures are consitleved in terms of the mechanisms by which the structure can change. The mechanisms considered include both small adjustments to the lnnzellar spacing due to the motion of lamellar faults, and catastrophic changes due to instabilities. It is concluded that stable growth occurs at or near the minimum interface undevcooling for a gizierz growth rate. The conseqrlences of the existence of a diffusion boundary layer at the interface are discussed. The experimental results for the variation of growth rate, undercooling, and Lanzellar spacing are cornpared with the theory. We believe that the theory presented in this paper provides an adequate basis for understanding the complex phenomena of lanzellar and rod eutectic growth. The growth of lamellar eutectics has been the subject of several theoretical and many experimental studies. The foundations for the theoretical work were laid by zenerl and Brandt2 in their analyses of the growth of pearlite. Zener estimated the effect cf diffusion, and took into account the surface energy of the lamellar structure. He found that the lamellar structure could grow in a range of growth rates at a given undercooling provided the lamellar spacing was appropriate for the growth rate. Since pearlite grows with only one growth rate and one lamellar spacing at a given undercooling, there is clearly an ambiguity in the theory. Zener removed this ambiguity by postulating that the growth rate was the maximum possible at the given undercooling. He predicted then that the product of the growth velocity v and the square of the lamellar spacing A should be constant, i.e., A2v = const. Brandt2 started out by assuming that the interface between the lamellae and austenite was sinusoidal. Because of this, the ambiguity encountered by Zener did not arise. Brandt was able to obtain an approximate solution to the diffusion equation, but, since he did not take into account the surface energy, his considerations are incomplete. Tiller3 applied some of these ideas to the growth of eutectics, and proposed a minimum undercooling condition to replace the maximum velocity condition used by Zener. These conditions are formally identical. Hillert4 extended the work of Zener. He found a solution to the diffusion equation assuming the interface to be plane. Taking surface energy into account, and applying Zener&apos;s maximum condition, he was able to calculate an approximate shape of the interface. Jackson et al.5 used an iterative method employing an electric analog to the diffusion problem to refine the calculation of interface shape. It was found that the interface shape calculated from a plane-interface solution to the diffusion equation was negligibly different from the exact solution. The method provided an analog only for eutectics for which the volumes of the two phases are equal, growing from a melt of exactly eu-tectic composition. There has also been considerable experimental work on eutectics, Several experimenters8-10 found that A2v is constant as predicted by Zener.1 Hunt and chilton10 demonstrated that ?T/v1/2 is also a constant for the Pb-Sn system as predicted. Lemkey et al.11have recently found A2v to be constant for a rod eutectic. In the present paper, we present the steady-state solution for the diffusion equation for a lamellar eutectic growing with a plane interface, for the general case, that is, with no restriction on the relative volumes of the two phases, and with the melt on or off eutectic composition. A similar solution is also found for a rod-type eutectic. Expressions are obtained for the average composition at the interface and the average curvature of the interface. These equations for the average composition and curvature are similar in form to those derived by Zener1 and Tiller,3 and provide a justification for some of the approximations made by these authors. The mechanisms by which the spacing in a lamellar structure can change are considered. The important mechanism for small changes in lamellar spacing involves a lamellar fault. Examination of the stability of lamellar faults leads to the conclusion that the growth occurs at or near the extremum.* The insta- bilities which can develop in a rodlike structure are also discussed, resulting in the conclusion that this structure also grows at or near the extremum. Comparison of the conditions for rod and lamellar growth permits a prediction of the surface-energy anisotropy required to produce rods or lamellae for various volume-fraction ratios. The diffusion equation predicts the existence of a diffusion boundary layer at the eutectic interface unless the eutectic has 0.5 volume fraction of each phase and is growing into a liquid of eutectic composition. This boundary layer is such as to make the composition in the liquid at the interface approximately equal to the eutectic composition. This boundary layer permits changes in composition during the zone refining of eutectics. Photographs of the eutectic interface of a growing transparent organic eutectic system have been made. Both the components of this eutectic are transparent organic compounds that freeze as metals do.12 The in-

Jan 1, 1967

By E. S. Fisher, L. C. R. Alfred

The elastic anisotropy factors, c4,/c6,, c3,/cll, and c12/cl,, for hcp metal crystals vary significantly among the dgferent unalloyed metals. Significant variations with temperature are also found. The effects of elastic anisotropy on the dislocation in an elastic continuum with hexagonal symmetry have been investigated by computing the elasticity factors for the self-energies of dislocations in fourteen different metals at various temperatures where the elastic moduli have been reported. For most of the metals the effects of the orientation of the Burgers vector, dislocation line, and glide plane are small and isotropic conditions can be assumed without significant error. Significant effects of anisotropy are, however, found in Cd, Zn, Co, Tl, Ti, and Zr. The elasticity factors have been applied in the calculations of dislocation line tensions, the repulsive forces between partial dislocations, and the Peierls-Nabarro dislocation widths. It is predicted that the increase in elastic anisotropy with temperature in titanium and zirconium makes edge dislocations with (a), (a + c), and (c) Burgers vectors unstable in basal, pyramidal, and prism planes, respectively. The probability of stacking faults forming by dissociation of Shockley partials in basal planes also decreases with increasing c4,/c6, ratio, when the stacking fault energy is greater than 50 ergs per sq cm. The widths of screw dislocations with b = (a) in titanium and zirconium increase very significantly in prism planes and decrease in basal planes as c4,/c6, increases. The effects of elastic anisotropy on various dislocation properties in cubic crystals have received considerable attention during the past few years. In the case of cubic symmetry the departure from isotropic elasticity depends entirely on the shear modulus ratio, A = 2c4,/(cl, —c12); i.e., the medium is elastically isotropic when A = 1. Foreman1 showed that an increase in the ratio A produces a systematic lowering of the dislocation self-energy for a given orientation and Poisson&apos;s ratio. ~eutonico~, has shown that large anisotropy can have a marked effect on the formation of stacking faults by the splitting of glissile dislocations in (111) planes of fcc and (112) planes of bcc crystals. ~iteK&apos; made similar calculations for (110) planes of bcc metals. Both studies of bcc metals showed that the large A values encountered in the alkali metals tend to reduce the repulsive forces between Shockley partial dislocations. In fcc metals, however, A does not vary over the large range encountered in bcc metals; consequently, the effect of A on the forces between Shockley partials is masked somewhat by the differences in Poisson&apos;s ratio between metals. The effect of A on the line tension of a bowed out pinned dislocation has also been investigated for cubic crystals, first by dewit and Koehler5 and more recent- ly by Head.6 In both cases the line energy model is applied and the core energy is not taken into account, thus making the conclusions somewhat tenuous with regard to the physical interpretation. Nevertheless, the fact that a large A decreases the effective line tension is clearly evident and the tendency for large A to produce conditions that make a straight dislocation unstable (negative line tensions) also seem evident. Head, in fact, shows visual microscopic evidence that stable V-shaped dislocations occur in 0 brasse6 For hcp metals the definition of elastic anisotropy is more complex and, furthermore, significant deviations from an isotropic continuum are found among a number of real hcp metals, especially at higher temperatures. The present work was carried out to survey the effects of elastic anisotropy on the elasticity factors, K, that enter into the calculations of the stress fields around a dislocation core. Some isolated analytical calculations have previously been carried out for several hcp metals but they are restricted in the dislocation orientations and temperature.8&apos;9 The present computations are based on single-crystal elastic moduli that have appeared in the literature and consider various orientations requiring numerical computations. The results are then applied to survey the effects of temperature on the dislocation line tension and dislocation splitting in hcp metals. PROCEDURE Anisotropy Factors. The degree of elastic anisotropy in hcp crystals cannot be described by a single parameter, such as the A ratio in cubic crystals. The following three ratios must be simultaneously equal to unity in order to have an elastically isotropic hexagonal crystal: The magnitudes of these ratios at several temperatures, as computed from the existing data for the elastic moduli of unalloyed hcp metals, are given in Table I. There are no cases of complete elastic isotropy, but the large anisotropy ratios encountered in the cubic alkali metals are also missing. There are, however, several significant differences among the hcp metals, the most notable being the relatively small A and B ratios in zinc and cadmium and the differences in the magnitudes and temperature dependences of A. It has been noted that the temperature dependence of A has a consistent relationship to the occurrence of the hcp — bcc tran~formation. For cadmium, zinc, magnesium, rhenium, and ruthenium, A is less than unity at 4&apos;~ and, with exception for rhenium, decreases with increasing temperature. In the case of rhenium, A has essentially no temperature dependence between 923&apos; and 1123"~, so that it is clear that A does not approach unity at higher temperatures. Cobalt is similar to the above-mentioned group of metals in that it also does

Jan 1, 1969

By W. Weissberger, Frankiewicz, L. Pommier

Introduction In the U.S., about one-quarter of the fuel oil and natural gas consumption is associated with power production in utility and industrial boilers and process heat needs in industrial furnaces. Coal has been an attractive candidate for replacing these premium fuels because of its low cost, but there are penalties associated with the solid fuel form. In many cases pulverized coal in unacceptable as a premium fuel replacement because of the extensive cost of retrofitting an existing boiler designed to burn oil or gas. In the cases of synthetic fuels from coal, research and development still have a long way to go and costs are very high. Another option, which appears very attractive, is the use of solid coal in a liquid fuel form - coal slurry fuels. Occidental Research Corp. has been developing coal slurry fuels in conjunction with Island Creek Coal (ICC), a wholly-owned subsidiary. Both coal-oil mixtures and coalwater mixtures are under development. ICC is a large eastern coal producer, engaged in the production and marketing of bituminous coal, both utility steam and high quality metallurgical coals. There are a number of incentives for potential users of coal slurry fuels and in particular for coal-water mixtures (CWMs). First, CWM represents an assured supply of fuel at a price predictable into future years. Second, CWM is available in the near term; there are no substantial advances in technology needed to provide coal slurry fuels commercially. Third, there is minimal new equipment required to accommodate CWM in the end-user&apos;s facility. Fourth, CWM is nearly as convenient to handle, store, and combust as is fuel oil. Several variants of CWM technology could be developed for different end-users in the future. One concept is to formulate slurry at the mine mouth in association with an integrated beneficiation process. This slurry fuel may be delivered to the end-user by any number of known conveyances such as barge, tank truck, and rail. Slurry fuel would then be stored on-site and used on demand in utility boilers, industrial boilers, and potentially for process heat needs or residential and commercial heating. An alternative approach is to formulate a low viscosity pre-slurry at the mine mouth and to pipeline it for a considerable distance, finishing up slurry formulation near the end-user&apos;s plant. Finally, at the other extreme of manufacturing alternatives, washed coal would be shipped to a CWM manufacturing plant just outside the end-user&apos;s gate. Depending on fuel specifications and locations of the mine and end-user facility, any of these alternatives may make economic sense. They are all achievable in the near term using existing technology or variants thereof. The Coal-Water Mixture CWMs contain a nominal 70 wt. % coal ground somewhat finer than the standard pulverized ("utility grind") coal grind suspended in water; a complex chemical additive system gives the desired CWM properties, making the suspension pumpable and preventing sedimentation and hardening over time. Figure 1 shows the difference between a sample of pulverized coal containing 30 wt. % moisture and a CWM of identical coal/water ratio. The coal sample behaves like sticky coal, while the CWM flows readily. The combustion energy of a CWM is 96-97% of that associated with the coal present, due to the penalty for vaporizing water in the CWM. Potentially any coal can be incorporated in the CWM, depending on the combustion performance required and the allowable cost. CWMs are usually formulated using high quality steam coals containing around 6% ash, 34% volatile matter, 0.8% sulfur, 1500°C (2730°F) initial deformation temperatures, and energy content of 25 GJ/t (21.5 million Btu per st). Additional beneficiation to the 3% ash level can be accomplished in an integrated process. There are a number of minimum requirements which a satisfactory CWM must meet: pumpability, stability, combustibility, and affordability. In addition, a CWM should be: resistant to extended shear, generally applicable to a wide variety of coals, forgiving/flexible, and compatible with the least expensive processing. It was found that a complex chemical additive package and control of particle size distribution are necessary to achieve these attributes simultaneously, while maximizing coal content in the slurry fuel. Formulation of Coal-Water Mixtures A major consideration in the manufacture, transportation, and utilization of a slurry fuel is its pumpability, or effective viscosity. Most CWM formulations are nonNewtonian, i.e., viscosity depends on the rate and/or duration of shear applied. Viscosities reported in this paper were obtained using a Brookfield viscometer fitted with a T-spindel and rotated at 30 rev/min, thus they are apparent viscosities measured at a shear rate of approximately 10 sec-1. The instrument does reproducibly generate a shear field if spindle size and rotation rate are held fixed. By observing the apparent viscosities of several slurries at fixed conditions it is possible to obtain a relative measure of their viscosities for comparison purposes. A true shear stress-shear rate relationship at the shear rates at which the CWM will be subjected in industry may be obtained using the Haake type and a capillary viscometer. These viscometers are used for specific applications. However, for comparison purposes, apparent viscosities are reported.

Jan 1, 1985

By W. Bonfield

The temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of polycrystalline Cu 1.9 wt pct Be have been measured for the solution treated condition, an intermediate condition containing G.P. zones and ?&apos; precipitate and the overaged ? precipitate condition, in the range from -58° to 200° C. A transition in micro -yield behavior and a large temperature dependence were noted for the intermediate condition, which are interpreted in terms of the interaction of glide dislocations with two differently sized zones. In comparison the microscopic yield stresses of the solution treated and overaged conditions were less sensitive to temperature variations and are satisfied by the Mott-Nabarro and dislocation bowing theories, respectively. A determination of the temperature dependence of the yield stress of a precipitation hardening alloy has provided a powerful tool for evaluation of the operative deformation mechanism. There is a marked contrast between the effect of temperature on the yield behavior of a metal containing coherent zones or intermediate precipitates, which can be "cut through" by mobile dislocations, and a metal containing a dispersion of noncoherent particles, through which dislocation "bowing out" is the dominant role of deformation.&apos; These studies have in general been confined to single crystals, as it was considered that similar experiments on polycrystalline material did not produce good data because of the lack of sensitivity with which the yield stress could be determined. However, this objection has been removed by the introduction of mi-crostrain techniques, with which the yield stress in polycrystalline materials can be measured to a strain sensitivity of 10-6. Such measurements have not only shown that the deformation of polycrystalline precipitation hardening alloys can be examined with the same detail as single crystals, but also that some unexpected results are obtained.&apos; In this paper the results obtained from a study of the temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of a polycrystalline Cu 1.9 wt pct Be precipitation hardening alloy (Berylco 25) are discussed. The temperature dependence of the alloy was measured for three different conditions: 1) The solution treated condition (a supersaturated solid solution of a containing ~12 at. pct Be3) which is obtained by water quenching the alloy from 800° C. 2) The condition of y&apos; intermediate precipitate, to- gether with some G.P. zones,&apos; which is produced after an aging treatment of 2 hr at 315°C from the solution treated condition. (The alloy was cold rolled to 40 pct reduction prior to aging to minimize grain boundary precipitation effects.)4 3) The condition with equilibrium ? precipitate structure2 which is developed after an aging treatment of 24 hr at 425° C. EXPERIMENTAL PROCEDURE Tensile specimens of gage length 1 in. and with rectangular cross section of 0.18 by 0.06 in. were prepared from the solution treated, cold rolled alloy and were either resolution treated for 1 hr at 800°C, followed by water quenching, or aged for 2 hr at 315°C and 24 hr at 425° C to produce the desired precipitate structures. The microstrain characteristics of the aged specimens were determined at temperatures from —58" to 200° C and those of the solution treated specimens from -58° to 30° C. Each temperature was controlled to ± 0.2°C, which was a level of stability sufficient to eliminate thermal expansion effects from the measurements (~1.2°C temperature increase produced an extension of 2 x 10-6 in.). The microplastic behavior of the specimens in the temperature range below 82" C was measured with a standard Tuckerman strain gage,5 while at temperatures above 82°C a modified Tuckerman gage with a reduced strain sensitivity (4 x10-6 in. per- in.) was used. A load-unload technique was used to establish values of the microscopic yield stress. The specimen was strained at a constant cross head speed of 2 x 10-2 in. per min to a given stress level, at which the total strain was measured. Then the specimen was immediately unloaded at the same rate and any residual plastic strain determined. This procedure was repeated for an increasing series of stress levels until the microscopic yield stress was established by a direct measure of the stress to produce a residual plastic strain of 2 x 10-6 in. per in. (It should be noted that, as reversible dislocation motion occurs at stresses less than the microscopic yield stress,2 the plastic strain rate at this level was not constant.) In an ideal test, the microscopic yield stress would be determined from a continuous stress-strain measurement, rather than from a load-unload sequence, in order to eliminate mechanical recovery effects.6 However, it was found experimentally that mechanical recovery was negligible in Cu 1.9 wt pct Be at small plastic strains for all the temperatures investigated, as the microscopic yield stress was independent of the number of load-unload cycles employed (i.e., the values measured for specimens subjected to different numbers of cycles was within the experimental scatter determined for specimens tested in an identical manner). Therefore, it is reasonable to consider the microscopic yield stress determined in the load-unload

Jan 1, 1969