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By R. L. Fullman

IN the investigation of metallurgical transformations and the relationships between microstructure and properties of metals, it frequently is desirable to obtain a measurement of the relative amounts of the various phases present and of the mean size of particles into which each phase is dispersed. The relative amounts of the phases can be measured by the classical methods of area, lineal, and point analysis,1-5 in accordance with the principle that the volume fraction of a phase, the fraction of a polished cross section occupied by the phase, the fraction of a random line occupied by the phase, and the fraction of randomly arrayed points occupied by the phase are all equal. The validity of this relationship depends only on the attainment of a truly random sample of area, length, or points, and not on the size, shape, or distribution of the particles constituting the phase. Smith and Guttman8 have derived a relationship between the interface area per unit volume S, and the measurable quantities L., the interface length per unit area on a cross section, and NL, the number of interfaces per unit length intersected by a random line. Their equation, Sv = — L8 = 2NL is also valid regardless of the distribution of particle sizes and shapes. In contrast to the situation concerning measurement of relative fractions of phases and of interface area, the measurement of particle sizes in opaque samples has not been subjected to a complete analysis. It has been common to measure some lineal or area dimension of particles on a polished cross section and to use the mean value as a qualitative measure of particle size. In the present paper, quantitative relationships are established among the various mean dimensions on a polished cross section and the actual dimensions of the particles present. Particles of Uniform Size Spheres: If a metal sample contains particles of a phase a dispersed in the form of spheres of uniform size, a polished cross section through the sample will reveal circular areas of phase a with radii from 0 to ?, the radius of the spheres. Consider a cube of unit dimensions to be cut from the sample. If a cross section parallel to one of the cube faces is examined, the average number of particles per unit area (N,) equals the number of particles per unit volume (Nv) times the probability p1 that the plane would intersect a single sphere positioned at random within the unit cube. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length 2r would lead to the plane intersecting the sphere, the probability of intersecting a single sphere is just 2r. N8= Nvp1 = Nd-2r [1] Applying the equality of area and volume fractions, the relationship is found between sphere size and average area s of uniform spheres intersected by a random cross section, 4 - f = NV V = Nr . — pra = N s = Nd . 2rs S = —pr2 [2] A similar analysis reveals the average traverse length across spheres of uniform size when random lines are passed through the sample. If a randomly oriented unit cube is cut from the sample and a randomly positioned line is passed through the cube parallel to a cube edge, the number of spheres intersected by the line (Nl) equals the number of spheres per unit volume times the probability p1 of the line hitting a single randomly placed sphere in the cube. Since possible positions of the line occupy unit area, and possible positions for which it will pass through the sphere occupy an area of pr2, the probability of the line hitting a randomly placed single sphere is pr2. NL = Nv p1 = Nvpr2 [3] Combining this relationship with the equality of volume and lineal fraction, the desired relationship is obtained between radius and mean lineal traverse length -i, for spheres of uniform size. 4 - - 3 l=4/3r [4] Circular Plates: Consider a sample containing particles of a phase a in the form of circular plates of uniform radius r and thickness t, where r >> t. If the plates are randomly oriented, as in a sufficiently large sample of a fine grained polycrystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the plates are not randomly oriented, it is necessary to randomize the orientation of the cross-sectional planes and traverse directions. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of plates cut by the cross-sectional plane per unit area is equal to the number of plates per unit volume times the probability of a plate intersecting a single randomly positioned and randomly oriented plate in the cube. If J is the component of the plate diameter in the direction normal to the cross-sectional planes, the probability of a plane cutting a single randomly oriented plate is equal to J, the mean value of J for all possible orientations of the plate. Let 4 be the dihedral angle between a plate and the cross-sectional plane, and let p?, d? be the probability that a plate makes an angle between 4 and ? + d? with the cross-sectional plane. Then for ran-

Jan 1, 1954

By R. Maddin

IN analyzing the relation between the orientation of new grains and that of the deformed matrix of axially extended and recrystallized single crystals of face-centered cubic metals, a two-stage rotation process" is generally used where the first rotation is made in order to account for an "adjustment of orientation to the environment of strain."&apos; It has been argued that in spite of the difference of orientation, which may amount to as much as 12" (in a brass),&apos; between the octahedral plane as observed in the parent lattice and in the recrystallized grain, it is believed to be a common plane in the sense that it constituted the nucleus in the parent strained crystal from which the new grain grew.&apos; A possible source of the deviation in orientations of a common pole in the new grain and that of the deformed single crystal matrix from which it has grown may be found in the distribution of strain resulting from the plastic deformation. It might be expected in view of the incongruent nature of shear&apos; that the perfection of the octahedral plane along which glide has occurred is disrupted and that this disruption constitutes the strain from which nuclei of new grains can grow during recrystallization. Evidence for the existence of strain along glide planes was first detected by Taylor" in 1927 and substantiated by Collins and Mathewson&apos; in 1940. In their investigations, however, the deformed single crystalline specimens (aluminum) were cut mechanically along the glide planes followed by mechanical polishing. X-ray exposures (glancing angle) of only 8 min with filtered radiation were used. It was later shown&apos; that this type of surface preparation did not remove with all certainty the mechanically disturbed surface. It was felt that a re-investigation of this phenomenon using more refined techniques might reveal a more correct extent of the strain resulting from the deformation which might correlate the deviation of the common pole of the recrystallized grain with the acting slip plane of the matrix crystal. In accordance with these thoughts, a single crystal of a brass (70/30 nominal composition) M in. in diam x 5 in. long, tapered as in previous experiments,&apos; was extended and carefully documented with respect to elongation and shear. Disks about % in. thick paralle&apos;l to the primary slip planes were cut from the specimen by means of an etch cutter." These disks represented volumes of the specimen which had been extended 0, 5, 10, 15, and 20 pct. Copper Ka monochromatic radiation was obtained by reflecting 35,000 v copper radiation from the c-cleavage face of a pentaerythritol crystal. The monochromatic radiation was collimated and led on to the disk set at the proper 0 angle for reflection from the primary (111) planes. The monochromatic beam was aligned in a plane containing the active slip direction. Following a 10 hr exposure at the theoretical Bragg angle, the disk was reset at 0 + 1°, 0 — 1", 0 + 2", 0 — 2", etc., until no Bragg reflection was obtained. The disk was then rotated 90" about its polar axis, and the same X-ray procedure was used. The results are shown in Table I. It may be seen from the results in Table I that the plastic deformation (20 pct elongation) produces fragments of the glide plane which are rotated or tilted as much as 25 " from the normal position on a purely block slip model. In addition to the large variation in 0 angle in the slip direction, there is a variation in 0 as much as 20" in the direction at right angles to the direction of slip, i.e., <110>. In view of the results shown, it may now be argued that the strain distribution finds its origin in the incongruent nature of the slip process.&apos; The use of the two-stage rotation process seems valid in attempting to explain the relation between the orientation of recrystallized grains and the matrix from which they have grown. Acknowledgment This work was sponsored by the ONR under Contract Number N6 onr 234-21 ONR 031-383. The author would like to thank N. K. Chen for reading and correcting the manuscript. References &apos;R. Maddin, C. H. Mathewson, and W. R. Hibbard, Jr.: The Origin of Annealing Twins. Trans. AIME (1949) 185, p. 655; Journal of Metals (September 1949). &apos;J. A. Collins and C. H. Mathewson: Plastic Deformation and Recrystallization of Aluminum Single Crystals. Trans. AIME (1940) 137, p. 150. eN. K. Chen and C. H. Mathewson: Recrystallization of Aluminum Single Crystals After Plastic Extension. Unpublished. 4 C. H. Mathewson: Structural Premises of Strain Hardening and Recrystallization. Trans. A.S.M. (1944) 38. :&apos;C. H. Mathewson: Critical Shear Stress and Incongruent Shear in Plastic Deformation. Trans. Conn. Acad. of Arts and Science, (1951) 38, p. 213. "G. I. Taylor: Resistance to Shear in Metal Crystals, Cohesion and Related Problems. Faraday Soc. (1927) 121. &apos;R. Maddin and W. R. Hibbard, Jr.: Some Observations in the Structure of Alpha Brass After Cutting and Polishing. Trans. AIME (1949) 185, p. 700; Journal of Metals (October 1949). &apos;R. Maddin and W. R. Asher: Apparatus for Cutting Metals Strain-Free. Review of Scientific Instruments (1950) 21, p. 881.

Jan 1, 1953

By B. C. Allen

The interface energies of chronzium, molybdenunz. hugsten, and their solid-solution alloys Cv-35Re, MO-33Re, and UJ-25Re were studied at 0.6 to 1.0 of the absolllte liquidus ter)zpe,vature using fiz&apos;e )izethods. Liquid surface tension, yv , was deter mined clsing the pendant-drop and drop-weight methods. Results are, respectizlely, 1700, 2370, and 2480 +100 dynes per ct for the rhernium -containing alloys and essentially the same as tlwse reported for liquid chro)riln, trolybdenum, and tungsten. Average solid slrjace energy, rsv< xias ))zeasured using tlre fiber-extetlsion method. The ratio of ysS, the acerage high-angle grain-boundary energy, to ySV cclas jolnd fronz grain-bolzdary grooue angles fort)zed at the surface in an inert atrfizosphere. Absolllte iute?:face energies were deterawined using ?nultip/rase equilibria involzing suitable liquids of known surface tension (tin, silver). Interpretation of the experimented results in view of pvobable tenzperatzcre, orientation, and purity effects giz,e the follouling approximations in ergs per sq ctn: ysv (i2lo. Mo-33Re) - 2100, ySS (Mo, Mo-33Re) - 800, rr (defornzation twins in MO-33Re at 1200"C) - 800. ysV (Cr. Cr-35Re) - 2400. YSS (CY, Cr-35Re) - 1000. Probably Ylv- YSV- 2500 for tungsten and W-25Re, giving yss (It&apos;, W-25Re) - 900. The interface energies of solid and liqid ch?&apos;omiu?.z, nolybdenu?rr, and tungsten are not geatly aff&apos;ected by rhenium and therefore are not a ttlajor factor in the ductili zing rhenium effect in Croup VI-A metals. THE interface energies of the refractory Group VI-A metals, chromium, molybdenum, and tungsten, are not well-established. The objective of this investigation was to study the liquid surface tension, solid surface energy, and grain-boundary energy of these metals and compare them to those found for the bcc solid-solution alloys, Cr-35e,&apos; 0-33e,&apos; and -25e. Five techniques were used to measure interface energies in high-purity polycrystal rod, wire, and sheet at 0.6 to 1.0 of the absolute liquidus temperature. The alloys were chosen to see if there was any connection between interface-energy behavior and the ductilizing rhenium effecL4j5 EXPERIMENTAL WORK Materials. A description of the materials used is presented in Table I. Chromium rod was prepared by arc melting iodide process crystals supplied by Chromallo Cor., hot extruding, and warm swaging to 0.63-cm-diam rod.6 The sheet was prepared by rolling as-extruded rod to 95 pct reduction in area from a hydrogen furnace at 800" to 900°C and surface grinding off 0.02 cm from each face. Cr-35Re rod was prepared by arc melting sintered rhenium powder and iodide chromium crystals, warm rod rolling to 50 pct reduction in area in cans, and swaging to 60 pct reduction in area at 1100" to 1200°C. Some of the rod was warm-rolled to sheet and then surface-ground. Portions of swaged chromium and Cr-35Re were further reduced by swaging and drawing to 0.013-cm-diam wire by the General Electric Co. Mo-33Re and W-25Re rod, sheet, and wire were provided by Chase Brass and Copper Co. The molybdenum sheet consisted of two lots, both essentially the same except for the carbon content. Liquid Surface Tension. The liquid surface tension of Cr-35Re, Mo-33Re, and W-25Re was measured by a combination of pendant-drop and drop-weight methods using techniques already decribed." Following out-gassing, molten drops were formed on the ends of centerless-ground Mo-33Re and W-25Re rods by electron bombardment at 5 x 106 mm. Similar drops were formed on outgassed Cr-35Re rods by induction heating under 1 atm of 99.995 pct Ar. Solid Surface Energy. Solid surface energy was measured by conducting microcreep experiments on molybdenum, Mo-33Re, chromium, and Cr-35Re wires at 2350°, 2306, 1550°, and 180O°C, respectively. In preparation, gage marks -2.5 cm apart and -0.001 cm deep were circumferentially scribed on the wire with a razor blade. Weights of the wire material were then attached. Five to seven reasonably straight wires were hung in a container made out of the wire material. The free end was placed through a small hole in the removable top and secured by bending a small portion 90 deg. The containers not only tended to provide vapor-solid equilibrium for the wires but also protected them from gaseous impurities. They were nominally 2.5 cm in diam by 5 cm high and were made from extruded chromium rod, Cr-35Re arc casting, molybdenum bar stock, or welded Mo-33Re sheet. After deg re as ing, the assembly was outgassed at a relatively low temperature to 2 x 10"5 mm and then recrystallized 2 to 8 hr at the creep temperature in a rhenium-element resistance furnace. The static argon atmosphere was gettered by tantalum radiation shielding. Specimen temperature was measured optically to 25"C using calibration with known melting points and blackbody conditions. The wires generally developed a stable bamboo-type structure according to Fig, l(b), (c), and (d) and retained their gage marks [upper portion of Fig. l(d)]. One or two of the weights were clipped off to provide a low load for the creep anneal. To minimize the possibility of bending or breakage, the wires remained attached to the top of the annealing container which was held to keep the wires vertical. The distance between gage marks was

Jan 1, 1967

By Edward J. Felten

Binary Cr-A1 alloys containing from 2.5 to 30 wt pct Al and 0.7 wt pct Y were heated in oxygen, air, and nitrogen between 1000" and 1200°C. The reacLivity of the alloys was found to be dependent both on the alloy composition nnd the nature of t he atmosphere. In oxygen, nllojs containing up to 15 to 20 wt pct A1 reacted to produce an external scale of Crz03 and a subscale consisting Predominently of Al203. Alloys contazning 20 to 30 wt pct A1 react in oxygen to produce an A1203 external scale and little m no subscale. The latter alloys were markedly more oxidation resistant than those of low alurninum content. In air, the alloys on which an external Crz03 scale was formed were found to be permeable to nitrogen ns evidenced by the copious amomts of chromium and aluminum nilrides observed ns part of the subscale. The reactizities in nir (or nitrogen) of these alloys increase <m their aluminurn contents increase. However, alloys on which Al,O, us an external scale is formed were nol culnerable to nccelerated attack in air, and no eltldence of nitvide subscnles were observed. For all alloys, yttrium serwed pYimarily to improve oxide adhrence. THE role of chromium in the oxidation resistance of Fe-Cr alloys &apos;-&apos; and that of aluminum in Fe-Cr-A1 al10s&apos; has received considerable attention in recent years. This is understandable since many of these alloys have excellent oxidation resistance due to the formation of either a Cr203 or a-Ala03 film between the metal and the oxidizing atmosphere. Small additions of yttrium or other rare earth metals are effective in preventing spalling of the protective oxide from the metal substrate."" In contrast, little is known regarding the oxidation resistance of Cr-A1 alloys, although some work has been done by Tumarov et a1.&apos; The poor niechanical properties exhibited by Cr-A1 alloys make them undesirable for use as structural components, but their use as coatings cannot be disregarded. The use of chromium-rich aluminide coatings for refractory metal alloys is an example of the potential use of this type of sytem. The purpose of this work is to examine the oxidation behavior of Cr-A1 alloys containing 2.5 to 30 wt pct A1 and 0.7 wt pct Y. The effects of temperature, atmosphere, and thermal cycling have been determined. EXPERIMENTAL PROCEDURE The alloys used in this investigation can be divided into two groups. Those containing 2.5, 5, 7.5, and 10 wt pct A1 and 0.7 wt pct Y were extensively evaluated in the temperature range from 1000" to 1200°C. Alloys containing 15, 20, 25, and 30 wt pct A1 and 0.7 wt pct Y were tested only at 1200°C. All of the alloys were prepared by standard arc-melting techniques in the form of cylinders approximately 4 in. long and 19 in. in diam. Wafers were cut from the cylinders and subsequently subdivided into rectangular coupons. The alloys were brittle and therefore some cracks were found in almost all specimens. The coupons were prepared for oxidation by mechanically polishing through 600 grit Sic paper, and were thoroughly degreased just prior to testing. Two types of oxidation experiments were conducted, namely; cyclic tests in which the specimens were examined and weighed after each 2 hr exposure, and continuous thermal balance tests run in a controlled atmosphere (oxygen, air, or nitrogen) for 20 hr. In the former test the spalled oxide was not included when the specimens were weighed. The physical condition of a specimen was noted visually after each cycle and testing was continued either to failure or until the performance of the specimen was well characterized. Both Micro and Semi-Micro Thermal Balances (Ains-worth) were used in the continuous tests. The oxidized specimens were sectioned and prepared for metal log raphic examination. The specimens were polished through 600 grit Sic paper. After polishing through 6 and l p diamond, a final mechanical polish with Linde B-Alz03 was used. Specimens containing 2.5 pct A1 were etched electrolytically using a 10 pct oxalic acid solution at 4 v for about 2 sec. Selected specimens were examined in the electron microprobe analyzer. Oxide specimens were examined by standard X-ray diffraction techniques. EXPERIMENTAL RESULTS For convenience, the test results have been broken down according to the exposure temperature, and further subdivided according to the type of test and atmosphere employed. Because of the poor quality of the specimens a larger than normal amount of scatter was observed in the measured rate constants. Also, the evaluation of the weight gain data was done on a somewhat arbitrary basis and may not be truly representative. However, the results obtained do show a significant trend in behavior regarding both alloy composition and the nature of the oxidizing atmosphere. I) Oxidation Behavior at 1000°C. A) Continuous Oxidation estsin Oxygen. This series of experiments was run in the Ainsworth Micro-Thermal Balance using pure oxygen at a pressure of 76 mm Hg. Under these conditions all specimens oxidized in accordance with the parabolic rate law over a major portion of the exposure time; the rate constants appear in Table I. The oxide formed externally on all specimens was predominantly Cr,O,, which was generally adherent. In some cases a slight amount of spalling in the form of a fine powder was noted. a-A1203 was observed as a subscale, along with Yz03 in all alloys. Alloys containing up to 7.5 wt pct A1 oxidize more rapidly than the Cr-0.7Y alloy.

Jan 1, 1970

By H. C. Fiedler

Heats of high purity iron containing 3.1 pct Si and be -tween 0.0003 and 0.0295 pct N were prepared by vacuum melting ad then pouring while in a nitrogen atmosphere with the pressure between 0 and 90 psi. Strip from a heat with 0.0184 pct N underwent complete secondary recrystallization during the final anneal. Heats with less nitrogen had too few Si3N4 particles to restrain normal grain growth, and the heat with higher nitrogen had too many particles to allow complete secondary recrystallization. In the hot-rolled structure, Si3N4 precipitates only at the grain boundaries, with the consequence that annealing after hot-rolling diminishes the ability to subsequently undergo secondary recrystallization. In contrast to this behavior, ALNprecipitates uniformly in the hot-rolled structure. Under 1 atm of nitrogen, Si3N, in 3.1 pct Si-Fe dissociates between 900" and 950°C; the solubility of nitrogen increases from 0.0010 pct at 900" to 0.0030 pct at 1200°C. The solubility of nitrogen in Si-Fe has been the subject of many investigations. Corney and Turkdogan1 heated a 2.83 pct Si alloy in nitrogen and found the solubility, under 1 atrn of nitrogen, to be 0.0019 pct at 900°C. They claimed that Si3N4 did not form in the alloy above 705°C in 1 atrn of nitrogen. Fryxell et al.2 heated samples of 3.25 pct Si-Fe containing 0.0025 pct N over a range of temperatures and then analyzed for total nitrogen by vacuum fusion and for nitrogen in solution by a modified Kjeldahl technique. At 900°C, they reported the solubility of nitrogen in equilibrium with Si3N4 to be 0.0011 pct. pearce9 found the solubility of nitrogen at 900°C under 0.95 atrn of nitrogen to be 0.0017 pct in a 3.06 pct Si alloy. He reported that Si3N4 does not form above 770°C in 1 atrn of nitrogen. Although internal friction measurements have given somewhat higher values for the solubility,4-6 if the solubility of nitrogen is as low as has been reported by most investigators, and if Si3N4 is stable up to at least 945°C at 1 atrn pressure of nitrogen as reported by Seybolt,7 a small amount of nitrogen in properly processed Si-Fe should be effective in promoting secondary recrystallization. The requirement is that in the final heat treatment there be enough small, well-dispersed particles of Si3N4 to restrain normal grain growth. Fast8 has obtained secondary recrystallization by nitriding high-purity 3 pct Si-Fe after hot-rolling to a thickness of 0.118 in., followed by processing to 0.012 in., and annealing. A large amount of nitrogen, 0.076 pct. was introduced during the nitriding heat treatment, but he has since reported9 that "a few hundredths of a percent" is sufficient. Small amounts of aluminum10 or vanadium" nitride are capable of promoting secondary recrystallization. Heats containing as little as 0.010 pct A1 or 0.042 pct V and from 0.006 to 0.009 pct N underwent complete secondary recrystallization at final gage, whereas heats with lesser amounts of aluminum or vanadium did not.l2 To be reported is the behavior of nitrogen in high-purity 3.1 pct Si-Fe, and the relation of this behavior to the ability to undergo secondary recrystallization. PROCEDURE Ingots weighing 1 lb were made by vacuum melting high-purity electrolytic iron (A104, Glidden Co.) and high-purity silicon (Monsanto Co.). The latter was used in preference to ferrosilicon to insure a low aluminum content. The design of the melting furnace permitted pouring with the furnace atmosphere either below or above atmospheric pressure. Accordingly, at the completion of melting, nitrogen was admitted to the desired pressure and the heat then immediately poured. The ingots were sound, with no indication of porosity. In Table I are listed the heats investigated, the nitrogen pressure at pour, and the nitrogen and oxygen contents as determined by vacuum fusion with a platinum bath at 1850°C, a procedure which insures measurement of the total nitrogen.13 In addition, all heats contained 3.1 pct Si and not more than 0.002 pct C, 0.003 pct S or 0.005 pct Al. It was subsequently found that the quantity of nitrogen contained in the heats in Table I does not necessarily represent that obtained under equilibrium conditions. For example, the ingot poured immediately after 1 atrn of nitrogen was admitted to the chamber contained 0.0093 pct N, whereas an ingot poured 3 min after the nitrogen was admitted contained 0.021 pct N and another poured after a 6-min delay contained 0.029 pct N. While some bleeding of the hot top occurred in the latter instance, the ingot when examined in cross section appeared sound. The ingots were heated to 1325°C in hydrogen and rapidly rolled to 0.080 in. in 3 passes. The roll speed of the final pass was reduced so as to increase the quenching effect of the rolls. The hot-rolled pieces were processed both as-hot-rolled and after heating for 3 min at 900°C in hydrogen. After cold-rolling to 0.026 in., the strips were heated for 2 min at 900°C in hydrogen, then cold-rolled to the final gage of 0.012 in. The loss of nitrogen in going from the ingot to cold-rolled strip was no more than 10 pct. The final heat treatment, which was for the purpose of develop-

Jan 1, 1970

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a&apos; phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a&apos; phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.&apos; Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a&apos;, with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a&apos; phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a&apos;. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By J. Szekely, P. Tarassoff, N. J. Themelis

In a copper converter air enters the bath in the form of turbulent jets. The interaction of these jets with the molten matte is fundamental to the converting process. In the present study, an equation is derived to describe the trajectory of a gas jet in a liquid. Calculated and experimental results for air jets injected into water are in good agreement. The trajectories of air jets in copper matte are predicted. THE air injected through the tuyeres of a Peirce-Smith copper converter emerges into the bath of molten matte in the form of a highly turbulent jet. The air jets affect a number of chemical and physical processes occurring in the converter: i) Converting Rate. It is generally recognized that the production capacity of a converter is limited by the flow of air which can be injected through the tuyeres and by the oxygen efficiency. In turn, the air flow is limited by pressure drop considerations or by the amount of splashing within the converter. ii) Oxygen Efficiency. This depends on the dispersion of the air jet in the liquid bath, and its trajectory through the bath. iii) Mixing. The jets act as mixing devices by transferring momentum energy to the bath; in this way the heat generated by the converting reactions occurring in the jets is distributed through the bath. iv) Refractory Wear. The proximity of the jets, which are centers of heat generation, to the refractories in the tuyere zone may have an important effect on refractory life. Mixing conditions in the bath will also influence refractory erosion. v) Splashing, and Accretion Build-Up. The energy of the jets is not dissipated entirely in mixing the bath. particles of liquid are carried out kith the gas above the surface of the bath in the form of liquid spouts and droplets. These result in the undesirable build-up of accretions on the converter mouth, and dust losses in the flue gas. Despite the importance of the interaction of the air jets and the matte in a converter, very few studies of the fluid dynamics of converting have been reported in the literature. Metallurgists in the USSR appear to have been more concerned with the subject than their Western counterparts. Deev et al.1 studied the interaction of an air jet with aqueous solutions in a converter model and qualitatively determined the tuyere air velocity and tuyere inclination which produced the most favorable results with respect to good mixing in the bath, and minimum splashing. Shalygin and Meyer-ovich2 also examined the air-matte physical interaction both in models and in industrial converters; they concluded that in conventional converting practice, there was no significant penetration of the air jets into the matte layer, and consequently the converting reactions occurred mainly in a zone adjacent to the tuyeres. The behavior of air jets in a converter bath, and the aerodynamic characteristics of tuyeres are discussed at length in a monograph on converting by Shalygin.3 However, the description of the phenomena occurring in the converter bath is largely qualitative. The side-blown Bessemer converter for steelmak-ing is very similar to the Peirce-Smith copper converter. Among the few investigations of the behavior of air jets in the bath of a Bessemer converter are those of Kootz and Gille4 who studied splashing in the course of an investigation on the effect of blowing conditions and converter shape on nitrogen pick-up in Bessemer steel. They found that during blowing standing waves were formed on the surface of the bath; the amplitude of the waves increased with the depth and angle of tuyere immersion until the whole bath moved backwards and forwards causing heavy splashing. Kazanstev5 used a model of a Bessemer converter to obtain correlations between the axial velocity of a gas jet and distance from the tuyere orifice and the Froude number of the jet. shalygin3 used these results to calculate the horizontal penetration of an air jet in a copper converter; the penetration was defined as the distance in which the axial jet velocity decreased to 10 pct of its initial value. However, the rising trajectory of the jet was not taken into account. In the absence of quantitative information on the fluid dynamics of converting, the design of copper converters has been based mainly on operating experience. Such experience tends to vary widely from smelter to smelter., This is reflected in Table I which is based on data compiled by Lathe and Hodnett.6 Aside from a rough, and perhaps obvious correlation between the total air flow and converter volume, Fig. 1, no pattern emerges from the data. For example, tuyere throat air velocities vary from 215 to 465 ft per sec in converters of the same size, for little apparent reason. The air jet energy input per cubic foot of converter volume, which may be taken as a measure of the amount of mixing in the converter bath, also varies greatly. A recent analysis of converter data by Milliken and Hofinger7 has also revealed unexplained variations in operating parameters. It is believed that by gaining a better understanding of the fluid dynamics of converting a more rational basis may be provided for the design of converters. In particular, it is proposed that if one takes into account the desirable criteria of a high converting rate, high oxygen efficiency and long refractory life, there should be an optimum configuration of tuyere air flow for a converter of a given diameter. The present investigation is concerned with the form and trajectory of an air jet in a converter bath. The general theory of turbulent jets has been expounded by Schlichting8 and Abramovich.9 However, most experi-

Jan 1, 1970

By V. Koump, T. F. Perzak, R. H. Tien

A series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts Mere measured during essentially one-dimensional freezing of Al-Cu alloys. The dimensions of the ingots were 3 by 5 by 6 in. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experitments. For each alloy the rate of heat removal was varied to give a total jreezing time in the range 3 to 30 min. The results of these measurements cowlpared favorably with the theoretical model of freezing of binary alloys with time-dependent surface temperature. IN engineering analysis of solidification of commercia1 steels and nonferrous alloys it is a common practice to assume that an alloy freezes by propagation of an isothermal solidification front, i.e., essentially as a pure metal. In two recent theoretical investigations&apos;j2 the present authors explored the possibility of a more realistic approach to the problem of solidification of alloys. In the proposed model the freezing of an alloy is assumed to take place by propagation of two isothermal fronts, i.e., the liquidus front and the solidus (or eutectic) front. The region between the two fronts contains both liquid and solid and is referred to as the solid-liquid region. The width and the solid content of the solid-liquid region vary with alloy type, solute concentration, and cooling rate. For a given alloy system, initial concentration of solute, and the mode of heat removal, the proposed model yields the temperature distribution within the solid skin, temperature, solid fraction, and concentration distributions with the solid-liquid region, and the rates of propagation of the liquidus and the solidus fronts. This model is obviously of considerable practical importance in engineering analysis of solidification processes, since it gives a more realistic estimate of skin strength during solidification and a better estimate of the total freezing time. Before the new model can be used with confidence, however, it is necessary to test this model experimentally. The experimental testing of the proposed model is a relatively simple matter since the effects to be measured are large and a relatively simple experiment will suffice. The theoretical model predicts, for example, that during freezing of an alloy containing substitutional type solute (negligible diffusion in the solid during freezing) the solid-liquid region occupies an appreciable portion of the ingot, even at low concentration of solute.&apos; Another prediction of the theo- V. KOUMP, formerly with U. S. Steel Corp., is now with Research and Development Center, Systems and Process Division, Westinghouse Electric Corp., Pittsburgh, Pa. R. H. TlEN is Senior Scientist, Fundamental Research Laboratory, U. S. Steel Corp., Research Center, Monroe ville, Pa. T. F. PERZAK, formerly with U.S. Steel Corp., is now with Fiber Industries, Greenville, S. C. Manuscript submitted March 6, 1968. IMD retical model, easily verifiable by experiment, is that the rate of propagation of the solidus (or eutectic) front increases as the solidus front approaches the center of the slab. This prediction is contrary to well-known behavior of the solidification front during freezing of pure metals, where the rate of propagation of the solidification front decreases with time and freezing is completed at the lowest rate. A rather severe test of the proposed model is provided by comparison of theoretical predictions and experimental measurements of the effects of cooling rate and composition on the rates of propagation of the liquidus and the eutectic fronts. In order to test the soundness of the formulation and the method of solution of the problem of solidification of alloys a series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts were measured during essentially one-dimensional solidification of A1-Cu alloys. The A1-Cu system was chosen strictly as a matter of convenience. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experiments. For each alloy the rate of heat removal was varied to give the total freezing time in the range 3 to 30 min. The results of these measurements are compared with the predictions of the theoretical model of solidification of binary alloys, with time-dependent surface temperature.&apos; Before the experiments described in this paper were undertaken, a serious attempt was made to utilize the measurements of previous investigators to test the theoretical model. In the course of this preliminary study a careful review was made of experiments of Pellini and coworkers3 and Doherty and Melf~rd.~ The measurements in Pellini&apos;s work were carried out using a steel containing at least four major components. Evaluation of the solid fraction-temperature relation for this steel (required in the theoretical model) is difficult and uncertain. Doherty and Melford, on the other hand, measured the solid fraction-temperature relation experimentally, but did not give sufficient data to explore the effects of composition and the cooling rates on solidification. Hence it was not possible to utilize these measurements to test our theoretical model. EXPERIMENTAL METHOD The experimental technique used in this investigation differs somewhat from the more conventional techniques employed in solidification studies. This technique was developed primarily to eliminate con-vective mixing in the molten metal caused by pouring of molten metal into the mold. In our experiments A1-Cu alloys were melted directly in the mold. The mold assembly used in solidification experiments is shown in Fig. 1. The mold was fabricated from *-in. stainless-steel sheet. The dimensions of

Jan 1, 1969

By E. J. Nielsen, P. R. Strutt

A study has been made of the progressive changes in the distribution of etch-pit structures occurring during high-temperature creep in copper + 7 wt pct Al single crystals oriented with a [113] tensile axis. The two equally stressed glide systems with the highest Schmid factor would be expected to form subboundaries of the type predicted by Kear.2 The alignments of etch-pits on sections parallel to different (111} planes consistent with these types of boundaries were not observed. However, they were consistent with planar subboundaries (on a macroscopic scale). From an analysis of Amelinckx1 it may be shown that stable cross-grid dislocation boundaries may form in the primary slip planes. These boundaries form when dislocations with a Burgers vector not in the slip plane move into the plane by combination of climb and glide. THE geometry of subboundaries formed by the interaction of dislocations of two glide systems has been analyzed by Amelinckx,1 and the particular types produced by deforming fee crystals are predicted by ear.&apos; In this paper types of boundaries which may be formed when climb as well as glide occur are discussed as this is relevant in high-temperature creep. It is assumed in the present investigation that the etch-pits observed in Cu + 7 wt pct A1 on surfaces parallel to {111} planes delineate the sites of dislocations. Although there is no direct evidence for this previous work on a-Cu/Al single crystals by Mitchell, Chevrier, Hockey, and Mon-aghan,3 would show this assumption to be reasonable. The alignments of etch-pits which form during creep are studied on sections parallel to each {111) plane. It is then deduced that these alignments are consistent with a specific type of planar subboundary. The Cu + 7 wt pct A1 single crystals had a [113] tensile axis and Fig. 1(a) shows schematically the relation of the slip planes and slip directions (as represented by tetrahedron ABCD) with reference to the tensile axis. The two equally stressed glide systems with the maximum Schmid factor namely ß-AD and (a-BD, from the analysis of Kear,2 would be expected to form the boundaries shown in Fig. l(a) and (b), also Fig. 5(a) and (b). EXPERIMENTAL PROCEDURE The a-Cu/Al single crystals were grown and annealed in a "gettered" argon atmosphere. Chemical analysis showed the aluminum content to be uniform in each crystal and the difference between crystals was maintained to an accuracy of ± 0.25 wt pct. The initial dislocation density and mean subgrain diameter after annealing was -106 cm-2 and 250 µ, respectively. Surfaces parallel to (111) planes were produced by specially developed electrolytic machining processes. The {111} faces were next electropolished for 5 min in a solution consisting of 25 g chromium trioxide, 113 ml glacial acetic acid and 40 ml water; the applied potential was 8 v. Dislocation etch-pits were revealed using l an etchant described by 1 ml bromine, 45 ml HCl, and - 250 ml water. RESULTS In crystals strained into secondary creep at higher stresses (443 and 750 g - mm-2 at 650° C aligned rows of etch-pits parallel to slip plane traces were evident in sections parallel to the (1111, (ill), and (111) planes, see Fig. 3. As well as the longitudinal alignments in Fig. 3, well formed randomly oriented arrays indicative of an equiaxed subgrain structure are evident. At the lower stresses (100 to 230 g . mm-2) only an equiaxed structure formed during creep. The sections in Fig. 3 are from a crystal crept for 70 hr at 650°C with a CRSS of 443 g.mm-2. Two identically oriented crystals were also deformed at the same temperature and stress for 5 min and 4 hr. In the crystal crept for 5 min, the etch-pits were randomly distributed with no tendency for directional alignment, see Fig. 2(a). As shown in Fig. 2(b) aligned arrays were evident after 4 hr creep but they were not nearly so well defined as in Fig. 3. The alignments (parallel to the arrows) in Fig. 3 are consistent with the existence of boundaries in the two main slip planes a and ß. The way in which this is deduced is seen by reference to Fig. l(c), where the existence of boundaries in the a and ß planes is verified by sectioning parallel to a,ß, and d. The (111) and ß(111) planes intersect the d(111) plane along BC [101 ] and AT [011] and alignments parallel to [101] and [011] are clearly evident in Fig. 3(c) in a section parallel to the d(111) plane. Similarly the a, and ß planes in Fig. l(a) intersect each other along DC [110] and hence there will be an alignment parallel to [110 ] in sections parallel to the a-plane and the ß-plane; this is evident in Fig. 3(a) and Fig. 3(b). It is interesting to note that alignments of etch-pits consistent with the boundaries predicted by Kear2 were not observed; see Figs. l(a) and l(b). The geometry of boundaries in {111} planes as shown in Fig. l(c) is discussed later. In Fig. 4(a) the individual etch-pits are resolved and the alignments are exactly parallel to the slip trace direction [101]. However, in some areas alignments deviate away from the slip trace direction by as much as 10 to 15 deg, this is evident in Fig. 4(b), and in Fig.

Jan 1, 1969

By P. R. Smith, R. A. Walters

Borates have been mined in the desert areas of California and Nevada for more than 100 years. To about 1890, playa surface mining provided the chief sources of boron minerals. Underground mining of colemanite and later of borax and kernite was predominate until about twenty years ago. Open pit mining of the large deposits of borax and kernite near Boron, California has been most significant for the past twenty years. Mining of colemanite in the Ryan, California area, near Death Valley, began in 1907. Following the discovery of the large deposits in the Boron area (about 1957), mining in the Death Valley area became nearly nonexistent. Only small tonnages were mined for special uses. Little mining was done in the Boraxo area near Ryan. The first claim was made in about 1915. In 1960 the area became the property of the Kern County Land Company, which was acquired by Tenneco Oil Company in 1967. In 1976 the various boiate properties and claims in this region were acquired by American Borate Corporation. The open pit mine is now approximately 122 m (400 ft) deep, 910 m (3000 ft) long and 305 m (1000 ft wide). The borates in the Boraxo pit consist primarily of three minerals. These are about 50% colemanite (CB6011 5H20), about 40% probertite (NaCaB50g 5H20), and 10% ulexite (NaCaBgOg 5H20). The colemanite, along with boric acid and high-grade colemanite ore from Turkey provide the only sodium-free borates for production of textile grade fiberglas. When heated to its decomposition temperature, colemanite decrepitates to a fine powder, which is the basis for the concentration process. The gangue minerals in this deposit are primarily calcite and clays, including bentonite. The ore body has a very low arsenic content, which is a desirable feature. Test work had been done with samples prior to the results discussed herein. This paper will discuss results of test work which were the basis for erection of a plant, and the subsequent plant operations. Laboratory Calcination and Air Tabling Tests Laboratory calcination tests showed that substantial upgrading of the borate could be accomplished by calcining followed by screening of the calcined material. Removal of the + 28 mesh calcine resulted in borate losses of less than 10% with a rejection of 40 weight % or more of the calcine. The minus 65 mesh calcine generally met the requirement of containing 48%, or more, B203. The minus 28 plus 65 mesh material contained an intermediate quantity of borate and would require additional treatment. Testing demonstrated that ore would not have to be reduced to a size finer than 19 mm (3/4 in.) prior to calcination. A temperature range from 400 to 455OC (750 to 850°F) was apparently satisfactory. Calcination at a temperature of 48Z°C (900°F), or higher, was unsatisfactory due to fusion. All laboratory calcination tests were static tests conducted by placing small covered charges in a laboratory furnace for 40 min. In all tests vapor issues from the furnace for 5 to 7 min. Following this period the ore could be heard "popping," due to decrepitation of the colemanite. The reaction generally continued for approximately one-half hour. Various size fractions of the calcination products from laboratory tests were subjected to laboratory air tabling tests, usually after removing the plus 28 mesh material. Laboratory air tabling tests were conducted employing a Whippet V-80 model air table manufactured by Sutton, Steele and Steele Co. now known as Tripple S Dynamics. Variables include both end and side-tilt, speed of vibration, and quantity of air rising through the deck. In addition to the variables in the machine itself, the feed rate is also a rather critical variable. Testing demonstrated that all - 28 mesh size fractions of the calcine could be successfully concentrated to 48% F2O3 or greater. For the finer material recoveries into the concentrate were between 85 and 90% of the borate. With the coarser material a substantial amount of middling was produced which required cleaner tabling. Laboratory calcination and air tabling tests indicated a process whereby the borate could be concentrated to about 50% B203 with borate recoveries approaching 90%. Moreover, the iron content of the concentrate was well below the required specification of 0.3% Fe2O3. Pilot Plant Calcination Following the laboratory test work described above, pilot plant testing was conducted to prove the process, provide data for engineering studies, and provide product for a prospective purchaser. The kiln used was 0.9 m-diam (3 ft) by 9.0 m (30 ft) long and had a belly section 1.2 m-diam (4 ft) by 2.74 m (9 ft) long near the discharge end. The kiln was operated at a speed of 0.7 rpm. Gas was fired into the kiln at an average rate of 27.1 m3/hr (958.4 cu ft per hr). The air to gas ratio used was 10:1. The ore was fed to the kiln countercurrent to the flame and discharged through a hopper into a screw conveyor which discharged to a 1.2 m (48 in.) Sweco separator. The separator had 28, 65, and 150 mesh screen cloths, with the plus 28 mesh fraction being discarded. The minus 28 mesh fractions were later subjected to air tabling. The exit gases, containing some calcine dust, were swept through two cyclones to recover the dust. The gases then were scrubbed in a Ducon scrubber; very little dust reported past the first cyclone. The dust from the first cyclone was also saved in drums. In addition to the gas rate, the flue gas velocity, after

Jan 1, 1981

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan&apos; presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner&apos;s contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-&apos; demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann&apos; and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,&apos; who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.&apos; In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/&apos; in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about &apos;/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.&apos; sturkey,&apos; however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.&apos; The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,&apos; but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970

RUSSIA was the United States Number One source of manganese ore in 1948 when 34 pet of imports were received from that source, stated Norwood B. Melcher, assistant chief, ferrous metals and alloys branch, Bureau of Mines. In 1949, this country received only 20 pet of 1948 shipments from Russia, and only token amounts are now being received. Aggressive programming by industry and government resulted in prompt increases in shipments from major, producing sources; India, Gold Coast, and the Union of South Africa all increased exports to fill the vacuum left by Russia and provided an excess adequate to increase total imports approximately 290,000 short tons in 1949. Again in 1950, and with, even less ore from Russia, imports increased another 290,000 short tons. Since the shift from Russia as a source of manganese, the United States has received in total about 85 pet of its imports from India, Union of South Africa, Gold Coast, and Brazil in that order of importance. Producers of both home consumed and merchant ferromanganese have been able to adjust downward the manganese content of the home-consumed product and so obtain partial relief. Millions of tons of steel were produced in 1951 with a relatively low grade ferromanganese. This adjustment has been made without decreasing the quality of the steel, although with some increase in cost through introduction of new problems, including increased hand- . ding of material and additional removal of carbon. Forced into a pattern of price and grade structure such as exists today, the producer of ferromanganese must adopt one of three possible courses as a short-range program: 1-He may continue to deplete his stocks by producing standard (78 pet) ferromanganese and hope that the future will bring some form of relief; 2-he may attempt to produce 78 pet ferromanganese by paying higher prices for premium ores; or 3-he may drop the grade of ferromanganese and stretch stocks and future supplies of ore as far as possible. The present rundown condition of Indian railroads is attributed to the fact that the service has had no opportunity to recuperate since the beginning of World War II, while the demand for the movement of commodities has probably increased. The Union of South Africa has expanded its exports to the United States greatly since 1948, but, the showing of that country in 1951 was disappointing. Efforts have been made for some time by firms in the United States, at the urging of the manganese miners in the Union, to prevail on the railroad authority to grant and make available larger allocations of cars for manganese ore movement. As a whole, such efforts have been unsuccessful. Although the allocation of rail shipping has been the obvious factor in the decreased movement of ore, many other less determinate factors appear to be involved. Brazil, long an important supplier of manganese to the United States, has important manganese deposits in three areas, all of which are significant to this country. The Gold Coast is an important source of supply. Its metallurgical ore is particularly of significance because of its unusually high grade which permits considerable latitude in blending with the lower grade materials of South Africa and India. The Belgian Congo should have an output of 100,000 tons or more annually beginning this year. R. S. Dean presented two papers. One with K. M. Leute on hydrometallurgical methods for recovery of manganese from domestic ores and one as sole author on the so-called carbamate or Dean process. The two papers tied into each other. In the first mentioned he reviewed the various processes applicable to oxidized, and nonoxidized and reduced ores. The advantages of each .were pointed out. So far the only process tried on a substantial scale on oxidized ores was the SO2 process used at Las Vegas, Nev., on Three Kids ore during World War II. Many problems were encountered. Some of them were whipped while some of those remaining perhaps would have been whipped had time permitted. Since then work has been done elsewhere to avoid the formation of the troublesome thionates encountered at the Three Kids plant. Dean discussed the thionate and NO, processes as applied to oxidized ores. The only commercially used process on reduced ores is that of making electrolytic manganese. Among others that have been considered are the nitric acid process, the Bradley-Fitch ammonium sulphate process, and Dean&apos;s ammonium carbamate process. Dean&apos;s thesis was that extremely large tonnages of so-called low grade manganese ores are available, and that these should not be depleted in attempting to simulate a foreign metallurgical grade ore. He pointed out that the grade of the domestic manganese ores would be considered high if the same grade were found in copper ores. The selling price of electrolytic manganese and electrolytic copper are roughly the same. In addition to electrolytic manganese, he believes that domestic ores should be used to make exceptionally high grade products. These might be battery grade oxide or substantially pure oxide sinter, which might be used for high manganese alloys or for upgrading metallurgical grade manganese to produce a high manganese ferroalloy. The carbamate process is based on the fact that manganous oxide is readily soluble in concentrated ammonia solutions containing ammonium salts. In solutions of sufficiently high concentration the manganese exists as an anion. Lixiviants of ammonia and ammonium carbonate permit extraction of the manganese from reduced ores and the manganese can be recovered as carbonate by heating or by driving off ammonia. R. V. Lundquist presented a paper on upgrading high-silica ores or concentrates with sodium hydroxide to extract silica and to yield a product with a more favorable manganese: silica ratio. The NaOH is, regenerated in part by CaO.

Jan 1, 1952

By D. T. Van Zandt

IN the late 1920&apos;s rotary drills began to replace the churn drills in the petroleum industry, but until the middle 1940&apos;s the churn drill was the only widely accepted means of drilling large-diameter blastholes for quarry operations. The Calcite plant of the Michigan Limestone Div., U. S. Steel Corp., was one of the first to experiment with rotary drills for quarry blasthole drilling, and the first to employ compressed air on a fully rotary rig to cool the bit and raise the cuttings to the collar of the blasthole. The Calcite plant operates a limestone quarry near Rogers City, Mich., in the northern part of the lower Michigan peninsula. The formation quarried, a portion of the middle Devonian series, is the Dundee limestone, which is uniform, seldom massive, and characterized by definite bedding planes. The dip is southeast, 40 ft to the mile. Quarry faces vary from 20 to 116 ft in height. Vertical blastholes are used entirely, from three to five rows of holes being drilled parallel to the working face, spaced 18 ft apart with 18-ft burden and drilled 6 to 8 ft below shovel grade. Quarry operations coincide with the navigation season on the Great Lakes, as the bulk of the stone is transported by lake carrier. The normal operating season runs from April to December, the remaining time being devoted to stripping operations and plant and equipment maintenance. In the followirig discussion drilling rates mentioned refer to overall drilling time and include all operations such as moving from hole to hole, penetration and extraction of tools, and routine maintenance. Time consumed by such factors as power delays and major machine repair is not included in drilling time unless otherwise stated. Figures cover only operations at this one plant in the formation mentioned. Needless to say, a very different set of figures could be obtained in a different formation. However, the comparison of footage obtained with churn drills and rotary rigs in this particular formation has been used as an indication of what might be the expected performance of rotary rigs in other formations. Prior to 1950 the bulk of the blasthole drilling at the Calcite plant was done by electrically powered churn drills. Both crawler and wheel-mounted rigs were used. These machines, which mounted a 22-ft drill stem of 4½ in. diam and a spudding type of bit 2 to 4 ft long, drilled a hole of 5 ?-in. diam. Average drilling rate of these rigs in the Rogers City formation was 8 % ft per hr. In 1946 one of the first rotary blasthole drills offered to the quarry industry was put into use on an experimental basis. This machine, known as the Sullivan Model 56 blasthole drill, Fig. 1, was on 16-in. crawler pads and electrically powered at 440 v. The drill bit, a Hughes Tri-Cone roller bit of 5?-in. diam, Type OSC, was threaded into the end of the 4-in. square hollow drill rod or stem. These drill rods were 20 ft long with female threads on one end and male on the other to allow for addition of the desired number of rods for drilling holes of various depth. Rods were handled by a single drum hoist geared to the main drive motor and racked by a 30-ft derrick or mast when not in use. The cable from the hoist drum fed through a crown block on the top of the derrick back to the water swivel mounted in the top end of the drill stem in use. This cable remained attached during drilling operations and was used to hoist the tool string from the hole. Down pressure was applied to the tool string by means of a pair of 4-in. diam hydraulic cylinders acting on the drill chuck holding the drill rod. The first chuck consisted of flat jaws which gripped the flat sides of the stem. These jaws were controlled by set screws forcing them into contact with the drill stem. As these set screws had to be loosened and tightened by hand with each stroke of the hydraulic feed cylinders, there was great delay. For this reason the semi-automatic chuck was developed which automatically gripped the stem on the downward stroke but released for retraction of the hydraulic feed cylinders. Rotation was imparted to the tool string by a rotary table acting on the chuck and geared to the main drive motor through a separate gear train and clutch. A positive displacement water pump, mounted on the drill, fed water through a system of pipes and hose into the water swivel mounted on the top of the drill rod and through the rod and bit, washing the drill cuttings to the collar of the hole. Where water was scarce, provision was made to settle out the cuttings coming from the collar of the hole and re-use the water. Where water was abundant the stream coming from the hole was wasted. Drilling rate with this machine was about 20 ft per hr and bit life 1600 ft of hole. While this rate was more than twice that obtained with the churn drills employed, the problem of water supply and drill cuttings disposal rendered the machine impractical from an operating standpoint. Consequently it was used only in that part of the operation for which water was easily supplied, when the character of the formation made it least difficult to wash cuttings away from the collar of the hole. In October 1949 it was suggested that drill cuttings be removed by compressed air, long used for this purpose on pneumatic drills, and collected at the collar by suction. Thereafter, the water pump on the Sullivan 56 was replaced by a 500-cfm air compressor and a trial run made. Air pressure at

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