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By R. Maddin, C. H. Mathewson, W. R. Hibbard

Recent publicationsl.2 establishing the presence of cross-slip in strained metallic single crystals oriented wholly within the area of single slip as predicted from the generalizations of Taylor and Elam3 described these markings as they appeared during the initial stages of the deformation process. At that time, the plane having a common glide direction with the primary slipping plane was reported as the cross-slip plane although the specific direction was not confirmed. Consequently, in continuation of the research, it seemed advisable to investigate the micro-graphic appearance of cross-slip together with the Laue back-reflection X ray analysis and stress-strain data during the later stages of the deformation process. Accordingly, a single crystal of brass (72.75 pct Cu, 0.01 pct Fe, 0.01 pct Pb, 27.23 pct Zn) was polished mechanically and repolished electrolytically after the manner described in the earlier paper.' Three pairs of flat surfaces, parallel to the specimen axis, and (1) perpendicular to the plane containing the pole of the primary glide plane and the specimen axis, (2) perpendicular to the plane containing the pole of the cross-slip plane and the specimen axis, and (3) perpendicular to the plane containing the slip direction and the specimen axis, were polished mechanically and repolished electrolytically, resulting in a final minimum gauge diameter of 0.4864 in. in a gauge length of 3.36 in. The specimen was elongated in tension and load-extension readings were taken following the method described in the initial investigation.' Observed reorientations were obtained from a series of Laue back-reflection photograms at the center and ends of the gauge length and at various positions around the circumference of the specimen. These were interpreted after the manner of A. B. Greninger.4 Cross-slip (Fig 1 and 2) was found with the first appearance of the primary slip clusters and usually joined members of these clusters. In addition, a third set of entirely different markings (Fig 3) could be noted. The displacement of this third set by the primary slip lines was measured as 8300 at. diam (3.04 microns). Since the specimen was carefully observed at high magnifications before any deformation and no markings of any type could be noted, it would appear that this third set was formed during the deformation process prior to the initiation of classical primary slip. Additional extensions produced no unusual change in the appearance of either cross-slip or the third set of markings. The number of lines increased with increasing elongation and appeared, generally, in areas where earlier markings were present. The continuity of the clusters of cross-slip lines in Fig 4, 5 and 6 illustrates that they are neither noticeably displaced by nor do they displace the primary lines at this stage. In Fig 7, cross-slip appears in a long narrow localized band approximately 45 degrees from the stress axis. This somewhat resembles a twin band except for the lack of a sharp boundary. After a shear of 0.257, suffcient additional glide occurred on the cross-slip plane to displace the primary slip lines (Fig 8). Generally, where a large number of cross-slip lines could be observed in an area on one flat surface, few cross-slip lines appeared on the diametrically opposite position on the parallel flat (Fig 9). These, of course, were not matched observations on the same glide ellipses. It was extremely difficult to make such comparisons. The third set of markings (Fig 10) was extensively displaced by glide on the primary slip planes. A plot of the width of primary slip clusters versus their displacement of the third set of lines is shown in Fig 11. The slope and the linearity of the plot suggest that each primary glide plane slips to a constant maximum value of shear before further slip is transferred to another plane. A shear value of 0.28 was determined in this case. Heidenreich5 has presented a similar schematic representation of glide for aluminum. After the specimen had attained an elongation of 51.8 pct, corresponding to a shear of 0.973, cross-slip appeared very prominently in certain areas as shown in Fig 12, yet at diametrically opposite positions very little cross-slip could be noted, Fig 13. Classical conjugate slip was found at this advanced stage in the deformation, Fig 14, which corresponds to the axial location shown at 12 in Fig 15. It should be noted that cross-slip occurs within the conjugate slip clusters and on the same plane as the cross-slip associated with the closely spaced primary lines which constitute a background in less distinct focus. The third set of markings noted at all stages in the deformation of the

Jan 1, 1950

By J. J. Gilman, T. A. Read

FOLLOWING the deformation 01 zinc monocrys-tals, sharply bent basal planes are observed near several types of inhomogeneities. Three of these in-homogeneities have characteristics which are quite regular so that they can be studied and analyzed. These are compressive kink bands, "deformation bands," and the inhomogeneities near end restraints. The present paper describes experiments in which "deformation bands" were artificially produced, and bend plane phenomena are discussed in terms of dislocation theory. Also, two new bend plane phenomena are described. The importance of bend plane phenomena in the deformation of crystals is not widely recognized. Many phenomena may be explained in a manner similar to the discussion in this paper. Jillson1 has pointed out that the "punching effect" in zinc is a bend plane phenomenon and is not caused by prismatic slip.' Bowles3 has suggested that they may be involved in diffusionless phase changes. Cahn4 has discussed the role of bend plane formation in the polygonization of zinc. Experimental Work Tensile Kink Bands: Because of the geometrical similarity between "deformation bands" and "kink bands" (compare Fig. 1 of this paper with Fig. 1 of the paper by Hess and Barrett"), the band shown in Fig. 1 of this paper will be called a "tensile kink band," and that shown by Hess and Barrett will be called a "compressive kink band." It is felt that the term "deformation band" should be reserved for banded structures in polycrystalline materials such as iron." Tensile kink bands seem to form spontaneously in aluminum crystals deformed by tensile loading.7-10 In zinc and cadmium crystals they do not form in good, carefully loaded specimens.'." However, tensile kink bands can be produced artificially in zinc crystals. The present authors did this by scratching one of the flat surfaces of triangular crystals transversely with a sharp needle. Natural tensile kink bands caused by inhomogeneities sometimes appeared in deformed crystals which were identical in appearance with the artificially produced ones. Zinc monocrystals were grown by the Bridgman method in graphite molds. Chemically pure zinc (99.999+ pct Zn) was used and the molds were sealed inside evacuated pyrex tubes during growth. The crystal cross sections were equilateral triangles with a typical base of 0.210 in. The artificial kink band shown in Fig. 1 is typical of tensile kink bands in zinc. The band lies between two bend planes which run from upper right to lower left and is inclined oppositely to the slip bands which are sharply bent at the two bend planes. The general form of the artificial tensile kink bands was independent of the scratch depth (1 to 5 mils deep) and also independent of which side was scratched. These variables did cause variations, however. Deep scratches produced more localized kink bands than light scratches. Also, if the angle between the slip plane traces and a transverse scratch varied appreciably among the three sides, then localization of the resulting kink bands also varied. Furthermore, if the slip direction lay nearly parallel to the scratched side, the band was more developed near the scratched side than at the opposite edge. Scratches produced tensile kink bands for crystal orientations from xo = 15" to x, = 75". Fig. 2 shows a scratched crystal after deformation. One triangular side lies in the plane of the photograph. The right hand tensile kink band was produced by a transverse scratch on the upper right side. The next two kink bands were the result of scratches on the front surface. The kink band at the left was caused by a scratch on the lower back side. All four bands have the same general form. A longitudinal scratch was also made on the crystal shown in Fig. 2 to determine the effect of a scratch on the critical shear stress. The critical shear stress of the scratched region was 33.9 g per sq mm compared to 24.4 g per sq mm for the un-scratched region above it. Fig. 3 shows Laue patterns of the crystal shown in Fig. 2. Fig. 3a shows the pattern of the undeformed crystal. The orientation was x, = 21°, A, = 31". After deformation, Fig. 3b was made of the homogeneously deformed portion of the crystal. The spots are compact but split into two halves. This region was elongated 45 pct and its orientation was x = 14", X = 20"; the sine law predicts x = 14", A = 20.5". Fig. 3c was taken near the center of the middle tensile kink band of Fig. 2. The pattern shows a range of orientations and polygonization in this region. The spread in orientation was due to the fact that the basal planes were curved (see Fig. 1) rather than flat as in the ideal case. Some may also have been the result of elastic distortions and "local curvatures." The orientation range was x = 23" to 32", A = 30" to 42". It is apparent from Fig. 3 that the material inside and outside the kink band rotated in opposite directions with respect to the tension axis during deformation. The orientation calculated from the ideal configuration of Fig. 9,

Jan 1, 1954

By P. E. Doherty, B. Chalmers

Subboundaries may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits do not form in the vicinity of high- or low-angle boundaries. They are attributed to the condensation of vacancies from a super saturation produced during coolirzg. Using the vacancy pit and Schulz X-ray techniques for observing low-angle boundaries, a study was made of the transition from the nearly perfect seed to the striated structuke characterist-ic of aluminum crystals grown from the melt. It was found that the individual striation boundaries develop by the coalescence of very small-angle boundaries, as well as by the addition of individual dislocations. Several mechanisms for the formation of striations are discussed. Evidence was found suggesting that a super-saturation of vacancies exists near a growing interface, and it is proposed that the resulting climb of existing dislocalions produces "half'-loops" at the interface, which combine to form the low-angle striation boundaries. LINEAGE, or "striation" boundaries, have been studied in detail by Teghtsoonian and Chalmers 1,2 in crystals of tin grown from the melt, and by Atwater and Chalmers3 in lead. They found that single crystals grown from the melt consist of regions which are separated by subboundaries that lie roughly parallel to the growth direction. A difference in orientation of 0.5 to 3 deg exists between the striated regions; the misorientation is such that the lattice of one region could be brought into coincidence with the lattice of its neighbor by a rotation about an axis approximately parallel to the direction of growth of the crystal. They observed an incubation distance for the formation of striations which increased with decreasing growth rate. They also found that in any crystal, the sum of all rotations of the lattice in one sense, in going from one striation to the next, is very nearly equal to the sum of all the rotations in the opposite sense. A striation boundary, which is a low-angle grain boundary, can be described as an array of dislocations. If it is assumed that suitable dislocations are introduced into the crystal during solidification, the formation of striation boundaries can be explained as a result of the migration of the disloca- tions into arrays. The formation of arrays is energetically favorable since the energy of an assembly of dislocations can be reduced by the interaction of the stress fields when a suitable array is formed. This investigation presents and interprets new information concerning the nature and origin of striation boundaries in aluminum. EXPERIMENTAL TECHNIQUE Single crystals of high-purity aluminum (Alcoa 99.992 pct) were prepared by horizontal growth from the melt.'' The specimens were subsequently electropolished in a solution of 5 parts methanol to 1 part perchloric acid kept between -10° and 0°C in a bath of dry ice and alcohol. The current density was approximately 6 amps per sq in. Doherty and Davis9 have shown that in aluminum sub-boundaries with misorientations of not less than several seconds of arc may be revealed by the vacancy pit technique. During cooling from elevated temperatures pits form on electropolished surfaces of aluminum crystals as a result of the condensation of vacancies.11 Pits do not form in the vicinity of small- or large-angle grain boundaries, presumably because such boundaries act as sinks for vacancies. Boundaries of misorientations down to 3 sec of arc are revealed as pit-free regions, see Fig. 1. The Schulz X-ray technique12 was used to determine the angular misorientations of subboundaries. In this method, white radiation from a micro-focus X-ray tube is used to produce an image of a fairly large area of a single crystal surface. Subboundaries cause splitting in the diffracted image, see Fig. 2. Misorientations down to about 15 sec of arc may be observed with this technique. OBSERVATIONS AND DISCUSSION Figure 1 shows a striated aluminum crystal grown at 10 cm per hr etched by the vacancy pit technique. An incubation distance of about 1 cm is observed before the initiation of striation boundaries. Fig. 2 is a Schulz X-ray photograph of a striated crystal similar to that shown in Fig. 1. A large area of the crystal was studied by means of a series of photographs. Fig. 2, which is a reflection from the (100) plane, included about the first 4 cm of crystal to freeze. There is an incubation distance of about 1 cm, and a distance of about 2 cm over which the angle of misorientation builds up to its final value of approximately one degree. Some twist component can be seen in Fig. 2 at the right side of the photograph. From Fig. 2 it can be seen that the sum of all rotations of the lattice in one

Jan 1, 1962

By Benny J. Nelson

AS a part of the fundamental research program of Aluminum Research Laboratories, some data were obtained on the ternary system Mg-Al-Mn. As very little information on the magnesium corner of this diagram has heretofore been published, it seems desirable to make available the values found for the liquidus and solidus surfaces of this system. Procedure The settling procedure was used for the determination of the liquidus compositions. Metallo-graphic examination of quenched samples, and stress-rupture upon incipient melting, were used for the solidus determinations. The settling procedure has been described in a previous paper.' Briefly, this method involved saturating the alloy with manganese at a temperature substantially above that at which the sohbility was to be determined, then cooling the melt to the latter temperature, and holding it at that temperature for a substantial period of time. Samples for analysis .were carefully ladled from the upper portion of the melt at hourly intervals during the holding period. After the ladling of each sample, the melt was stirred to redistribute some of the manganese that had already settled, because it appeared that when the latter particles of manganese again settled, they aided in carrying down more of the manganese and thus hastened the attainment of equilibrium. The melts were prepared and held in a No. 8 Tercod crucible holding approximately 4 lb of metal. The manganese was added either in the form of a prealloyed ingot (Dow M) containing about 1.5 pct Mn or by the use of a flux (Dow 250) containing manganese chloride. In calculating the flux additions, it was assumed that the manganese introduced would be equal to 22 pct of the total weight of the flux. Temperatures were measured with an iron-constantan thermocouple enclosed in a seamless steel tube, the lower end of which was welded shut. This protection tube also served as a stirring rod. The samples ladled from the upper portions of the melts at the various intervals were analyzed for aluminum, manganese, and iron. When making the alloys which were to be used for the determination of the solidus, 2½ in. diam tilt mold ingots were cast, scalped to 2.0 in. in diam, and extruded into ? in. diam wire. The principal impurities in the melts for this investigation were iron and silicon; their total not exceeding 0.03 pct. Portions of the wire, approximately 2 in. in length, were enclosed in stainless steel capsules for protection from the atmosphere. Bundles of these capsules, with a dummy capsule containing an iron-constantan thermocouple, were heated inside a large steel block (acting as a heat reservoir) in a closed circulating-air type electric furnace. At ap- propriate times, the capsules were removed and quenched in water. The wires were examined metallographically to determine the temperature of initial melting. Short times at temperature were used at the beginning for wire specimens of all alloys to obtain quickly the approximate temperatures at which melting could be first observed. When approximate solidus temperatures had thus been determined, equilibrium heating was attempted. This equilibrium heating consisted of an 8 or 16 hr period at a temperature, about 50 °F below the lowest temperature at which melting occurred when short heating cycles were used, followed by further heating for 1 hr periods at consecutive 10" higher temperatures. The theory for the method of stress-rupture at incipient melting has been well covereda and its limitations are recognized. Thus, if the interfacial tensions are such that the first minute quantity of liquid is "bunched up" at the grain boundary junctions instead of spreading out along the grain boundaries,³ temperatures higher than the solidus are required before melting will be manifested by rupture of the specimen. This point will be elaborated later. Specimens of the wires with a reduced section (approximately 1/16 in. diam) were suspended vertically in a tubular furnace. The setup used is shown in Fig. 1. The clamp holding the specimen was made from alumel thermocouple wire and the thermocouple was thus completed across the specimen by attaching a chrome1 wire to its lower end. Temperatures were read from a Speedomax recorder used in conjunction with a calibrated thermocouple. The small weight attached to the specimen and a vibrator attached to the furnace tube, to aid in distributing the molten constituent along the grain boundaries, were used to bring about rupture at a temperature closely approximating the solidus. The specimens were heated at a rate of about 5°C per min. The rupture of the specimens was indicated both by sound and by the action of the recorder. An argon atmosphere containing a small amount of SO² was used for protection of the specimen. The assembly was taken out of the furnace immediately following rupture and the specimen removed. Some of the broken specimens were examined metallographically and will be referred to later. Results and Discussion Fig. 2 shows a set of typical time-composition curves for liquid samples of the Mg-Al-Mn alloys used for the settling tests. The data as presented

Jan 1, 1952

By C. D. Hall, F. E. Dollarhide

Conventional static tests of fluid-loss agents do not realistically simulate conditions in a fracturing treatment. The dynamic tests reported here show that fluid-loss volume is better represented as proportional to time, rather than as the square root of time. This leads to a different equation for fracture area. The leak-off rate increases with increasing shear rate at the fracture wall, but appears to approach a limiting value. Pressure effects are minor. Spurt loss ordinarily is not affected by the flow velocity in the fracture and is inversely proportional to concentration of agent. The filter cake, once it is well established, is resistant to damage by the flow of plain fracturing liquid (without fluid-loss agent). The latter two findings indicate that a treatment employing a high-concentration spearhead followed by plain fluid can offer a more economical treatment under suitable conditions. INTRODUCTION The successful design of hydraulic fracturing treatments depends on accurate knowledge of the fluid-loss properties of the fracturing fluid. Howard and Fast,' in giving the basic equation relating fracture area to fluid and treating parameters, described three mechanisms which might control the rate of fluid leak-off from the fracture. One mechanism usually is dominant in a given well treatment. For each mechanism, the leak-off velocity is inversely proportional to the square root of time, and the proportionality constant is designated as the fracturing-fluid coefficient. For the wall-building type of fluid-loss agent, the coefficient is determined by a filtration test in a pressure cell, usually with a rock wafer or core as the filter medium. In these static tests, the cumulative volume generally is proportional to the square root of time, after an initial spurt volume. The static-fluid-loss test is not representative of the con,-&tions under which a fluid-loss agent performs in a fratturing treatment. The marked difference between the dynamic- and static-fluid-loss behavior of drilling fluids reported in the literature2,3 implies that dynamic testing is also needed with fracturing fluids. We have therefore undertaken a study of the dynamic-fluid-loss behavior of fracturing fluids. The testing apparatus has also afforded opportunity to evaluate the resistance of the filter cake to removal or damage by flowing fluid containing no fluid-loss agent, with and without sand. The results of these studies offer a means for more accurate evaluation of fluid-loss agent performance, and point the way to a "spearhead" fracturing technique which may offer more economical treatment for some wells. EXPERIMENTAL METHODS The dynamic-fluid-loss testing method is applicable to any type of wall-building fracturing fluid. The present study aimed first at finding what phenomena are involved, and therefore has been limited in the number of materials tested. All of the results specifically reported herein are for kerosene containing a commercial solid fluid-loss agent, which is commonly used at 50 lb/1,000 gal of oil. Another agent in liquid form, used usually at 20 ga1/1,000 gal oil, has shown all the same phenomena in dynamic tests, and generally the same level of fluid-loss control as the solid agent. The dynamic-fluid-loss core cell used in all tests is shown in Fig. 1. The fracture was simulated by the an-nulus between a 2.03 in. OD sandstone core and the surrounding pipe. Annulus widths of 0.234 and 0.117 in. were used, and the core was 3.5 in. long. The annular geometry provides a uniform fluid velocity and a well-defined shear rate over the entire filtering surface, and permits a large filter area (144 sq cm) in a reasonably compact cell. The leak-off fluid passed into a 0.5 in. diameter axial hole in the core. A hollow steel rod through this hole was threaded into a rounded "streamliner" upstream of the core, and into a mounting stud downstream. The streamliner and the stud had the same outside diameter as the core. In all tests except those where sand was circulated, the mounting stud had protruding rings which constricted the annulus, to minimize any tendency for channeling of the fluid to the side exit port. The ends of the core were sealed by Neoprene, steel and Teflon washers. The leak-off fluid was conducted from the hollow rod to an exit tube, through a metering valve (a fine-pitched needle valve) and a quick-opening toggle valve in series, and into graduated cylinders for volume measurement; Two separate circulating systems were used in the experimental program. The extensive initial testing was done at 50 to 150 Psi. The fluid was circulated by a variable speed Moyno pump, and the flow rate was read by a rota-meter flow meter. The filtration Pressure was supplied by holding a back-pressure with a throttling valve. The discharge streamcould be diverted into any of four sections

Jan 1, 1965

By O. B. Bennett

WHEN diamond drilling was introduced in the Rhokana mines in 1939 it was used principally for pillar removal and for completion of the upper portions of shrinkage stopes which were being affected by increasing pressure. This method of drilling long blastholes proved so successful that it was extended gradually to cover stoping, pillar recovery, and hanging cave work. BY 1949 virtually all the ~roduction of Mindola and Nkana was being obtained by this method. At the present time 87,500 ft are drilled each month by the 80 diamond drills in daily operation. Responsibility for control and issue of diamond drilling equipment and crowns, as well as tabulation of all performance figures, was taken over by a sPecially formed Roto drill department, which also investigated the problems encountered with this new method. To assist this department a fully equipped test chamber, Fig. 1, was established underground where performances of various types of machines and equipment could be studied under conditions as nearly uniform as possible. Since the establishment of this department, which was eventually taken over and incorporated into the study department, considerable experimental work has been done on every aspect of the subject. The problems can be classified broadly under four headings: improvement of drilling equipment, crown design, machines, and stoping layouts. One of the major problems with drilling equipment has been to eliminate vibration. Owing to flexing of rods in the hole, severe friction is set up on the back end of the 'Ore barrel and On any high spots in the rods, inducing harmonic vibration in the string of rods and causing the crown to chatter against the face. This not only causes premature crown failure but also reduces penetration speeds and increases wear on the machines and rods used. In the early days, when only holes of EX size were drilled, vibration was largely overcome by periodic greasing of rods and core barrel during each run, but with the change-over to the larger BX hole it became obvious that application of grease by hand was inefficient and time-consuming, and attempts were made to perfect a self-lubricating core barrel. A series of these core barrels was made up and tested and a number of the latest type were used under normal operating conditions, but although footages up to 120 ft were drilled without refilling the overall performance was inconsistent, and the idea was shelved in view of the success of the stabilizer rods referred to later in this paper. At the same time tests were made with barrels 5 ft and later 6 ft long instead of the normal 2 ft. Although a slight improvement was noticed, greasing was still necessary. It was found that rod vibration increased as the core barrel became worn, and in an early test chamber experiment crowns drilled with a worn core barrel averaged 95 ft with a diamond loss of 4.76 carats, whereas the same type of crowns with a new barrel averaged 228 ft with a diamond loss of 3.13 carats. until then all BX drilling had been done with B-sized rods, but during a test on a string of BX-sized rods it was noticed that vibration was negligible. Because of the larger surface area of metal bearing on the sides of the hole, however, the friction and resistance of rods of this size rendered them impracticable on any but the most powerful of the machines, The use of stabilizers spaced evenly along the rods was the next logical step, and for this B couplings, see Fig. 2, were set with three tungsten carbide inserts 1 in. long placed around the periphery equidistantly and at an angle of 45" with a right hand lead. These were placed immediately behind the core barrel and then at 12-ft intervals, as it was found that vibration still occurred when the stabilizers were more than 15 ft apart. The effect of these stabilizers was immediately noticeable; holes were drilled with a minimum of vibration, penetration speeds were improved, and as it was no longer necessary to grease the rods there was a marked decrease in the overall drilling time for each hole. While tests were being made with the stabilizer comeb periodic were taking place with a set of tapered threaded rods, and because there was marked improvement in efficiency it was decided to incorporate the stabilizers and tapered threading in all new rods ordered for Rhokana. The feature of these rods is that only four full turns are required to tighten the coupling as against nine for the present type of B rods. Also, as they are self-centering it is virtually impossible to crossthread them. Each rod has a male 5" tapered Acme thread, Fig, 3, on one end and a female at the other, so that separate couplings are unnecessary, and every fifth rod has an

Jan 1, 1955

By C. A. Winkler, V. Hospadaruk

PREVIOUS papers from this laboratory have discussed the effect of chloride ion on the cathode polarization during electrodeposition of copper from copper sulphate-sulphuric acid electrolytes, in the presence and absence of gelatin. The steady state polarization'" was found to decrease sharply and pass through a minimum with increasing chloride ion concentration in the presence of gelatin. The minimum shifted to higher chloride ion concentrations and to higher polarization values with increase in current density or gelatin concentration, while an increase of temperature shifted the minimum toward lower halide concentrations and lower polarizations. Since these observations were made in acid-copper sulphate electrolytes that contained no other addend than gelatin, there was obviously the possibility that they were not applicable to deposition of copper from commercial electrolytes that contain a variety of other substances in relatively small amounts. In particular, it was of interest to determine whether the presence of arsenic, antimony, or bismuth in the electrolyte would materially alter the behavior. Experiments have now been made under a variety of conditions with systems containing these cations, and the results are summarized in the present paper. Experimental Polarization measurements were made at 24.5oC in a Haring cell in the manner described previously.' Electrolytes were made with doubly-distilled water, and contained 125 g per liter of copper sulphate and 100 g per liter sulphuric acid, both of reagent grade Eimer and Amend gelatin from a single stock was used throughout. Chloride ion was introduced as reagent grade sodium chloride, and arsenic, antimony, and bismuth by dissolving the chemically pure metal in hot concentrated sulphuric acid and adding appropriate amounts of the solutions to the electrolyte. Each cathode, of 1/16-in. thick rolled copper, was first etched in 40 pct nitric acid and washed thoroughly with distilled water. The surface was then brought to a standard condition4~9 by electrodeposition from an acid-copper sulphate electrolyte containing no gelatin, at a current density of 3 amp per sq dm for 30 min, followed by deposition at a current density of 2 amp per sq dm for l hr. As in previous studies, the cathode polarization eventually attained a steady-state value (15 to 75 min) such that further change in polarization did not exceed 0.2 mv per min. The polarization values recorded are those for the steady states. "Excess weights" were determined with arsenic and antimony present in the electrolyte, as the difference between the weights of the deposits obtained in the presence of these cations and those obtained in their absence, with the two cells connected in series. When gelatin was present along with the arsenic or antimony, it was also added to the electrolyte in the cell in series. Results and Discussion The results of the study are summarized in Figs. 1 to 6. From Fig. 1, top, it is evident that the presence of arsenic or antimony alone results in an increase of polarization, while bismuth alone causes a decrease. The presence of gelatin (25 mg per liter) rather drastically modifies all three cation effects, as indicated in the lower panels of the same figure. The addition of chloride ion, when no gelatin is present, causes comparable decreases in polarization in the presence of antimony and bismuth, but a relatively larger decrease when the electrolyte contains arsenic. It is interesting to note that the decrease in polarization brought about by addition of chloride when both arsenic and antimony are present parallels the behavior with arsenic alone, while the polarization in the electrolyte containing the cation mixture, without chloride added, corresponds to that for an electrolyte containing only the antimony cation. Similarly, the polarization at zero concentration of chloride in electrolyte containing arsenic and bismuth is that corresponding to an electrolyte containing arsenic alone. From Figs. 3a, 4a and 4b, it is clear that, in the presence of gelatin at a level of 25 mg per liter, the effect of chloride in the presence of arsenic and antimony, or a mixture of the two, becomes quite analogous to that observed in the absence of added cations. When both bismuth and gelatin are present (Fig. 5), the decrease in polarization with increased chloride concentration is virtually absent. This is perhaps a reflection of the large decrease in polarization brought about by the bismuth itself in the presence of gelatin. The shifts of the minimum in the polarization-chloride concentration curves brought about by changes of temperature (Fig. 3b), gelatin concentration (Figs. 3c and 4c) and current density (Fig. 3d) when the metal cations were present are all similar to the corresponding shifts observed in their absence." The approximately linear "excess weightv-anti-mony concentration relation recorded in Fig. 6 would seem to indicate that antimony is codeposited with copper to a considerable extent. On the other hand, only very limited amounts of arsenic appear to be adsorbed or codeposited.

Jan 1, 1954

By M. T. Simnad, G. Derge, I. George

Measurements of current efficiency on iron-silicate slags in iron crucibles showed that conduction is about 10 pct ionic in slags with less than 10 pct silica and about 90 pct ionic in slags with more than 34 pct silica, increasing linearly in the intermediate range. The balance of the conduction is electronic in character. Silicate ions are discharged at the anode with the evolution of gaseous oxygen. Transport experiments show that the ionic current is carried almost entirely by ferrous ions, which may be assigned a transport number of one. THERE has been increased evidence in recent years that the constitution of liquid-oxide systems (slags) is ionic.1-3 The principal studies designed to establish the structure of liquid slags have been by electrochemical methods', " and conductivity measurements1,6,7 which also have indicated the presence of semiconduction in several silicate systems1,4-0 and in pure iron oxide.' It is well known that many slag-forming metallic oxides have an ionic lattice type in the solid state, and their properties are determined to a large extent by the lattice defects and ion sizes. As Richardson8 as pointed out, the detailed models of liquid slags cannot be found on thermodynamic data only but "must rest on a proper foundation of compatible structural and thermodynamic knowledge, combined by statistical mechanics." A careful thermodynamic study of the iron-silicate slags has been carried out by Schuhmann with Ensio9 and with Michal.10 They obtained experimental data relating equilibrium CO2: CO ratios to slag composition and made thermodynamic calculations of the activities of FeO and SiO, and of the partial molal heats of solution of FeO and SiO2 in the slags. It was found that the activity-composition relationships deviate considerably from those to be expected from an ideal binary solution of FeO and SiO2. However, the partial molal heat of solution of FeO into the slags was estimated to be zero. Their experimental results were correlated with the constitution diagram for FeO-SiO2 of Bowen and Schairer,11 with the results of Darken and Gurry" on the Fe-O system, and with the work of Darken"' on the Fe-Si-O system. All these studies were found to be consistent with one another. The variation of the mechanism of conduction with composition in the liquid iron-oxide-silica system in the range from pure iron oxide to silica saturation (42 pct SiO2) in iron crucibles was reported in a preliminary note." The current efficiency, or conformance to Faraday's law, showed some ionic conductance at all compositions, the proportion increasing with the concentration of silica. The current-efficiency experiments since have been extended. Furthermore, transport-number measurements have been completed in silica-saturated iron silicates to determine the nature of the conducting ions. Experimental Current Efficiency in Liquid Iron Oxide and Iron Silicates using Iron Anodes: This study was carried out by passing direct current through slags in the range from pure iron oxide to iron oxide saturated with silica (42 pct silica), using pure iron rods as anodes and the iron container as the cathode. A copper coulometer was included in the circuit to indicate the quantity of current passed during electrolysis. Assuming that the cation involved is Fe-+, the theoretical quantity of iron lost from the anode according to Faraday's law may be calculated and when compared with the actual loss observed, gives an indication of the extent to which Faraday's law has been obeyed. It also gives an indication of the presence and extent of ionic conduction in the melt. Preparation of the Slags: About 100 g of chemically pure Fe,O, powder is placed in an iron pot which is heated by induction until the contents liquefy. In this way, FeO is produced according to the reaction Fe2O3 + Fe = 3 FeO. More Fe2O3 or SiO, powder is added and, when a sufficient quantity of molten slag is obtained, the induction unit is turned off, the pot withdrawn, and the molten slag poured on to an iron plate. Homogenization and Electrolysis of the Slag: Apparatus—After considerable development, the setup illustrated in Fig. 1 proved to be quite satisfactory. A is an Armco iron cylinder, 1 in. ID and 1/8 in. wall, consisting of three sections placed one on top of the other. The bottom section is a pot about 5 in. long with a small hole drilled in its bottom to allow withdrawal of gases during evacuation of the apparatus. The middle section is 6 in. long and consists of a pot which serves as the slag container, while the top section is a hollow-cylinder continuation of the slag-container pot. The height of this latter section is about 5 in., giving an overall length of approximately 16 in. The iron cylinder is constructed in this way for ease of fabrication, the individual sections becoming welded together after the

Jan 1, 1955

By Murray F. Hawkins, W. J. Ainsworth

In all types of subsurface pressure gauges the extension which occurs in the pressure-sensitive element is a function of the difference between the external (well or calibration) pressure and the internal pressure within the gauge, rather than a function of the external pressure only. The internal pressure is near atmospheric and depends upon (a) the quantity of air sealed within the gauge at the time of calibration or measurement, (b) the quantity of moisture (liquid water), if any, sealed within the gauge, and (c) the temperature at which the calibration or well measurement is made. Part of this correction for the change of internal pressure with temperature is taken care of by the customary temperature coefficient of the gauge. However, part of it is not, and while this portion may be only a few psi, it is nevertheless predictable or preventable, and should be considered in precision measurements. ERROR NO. 1 If air is sealed in the gauge at the same temperature and pressure for both the calibration and the well measurements, the usual temperature correction will take care of any difference between calibration and well measurement temperatures. However, if air is sealed within the gauge at temperature T1 and pressure P1 at calibration but at temperature T2 and pressure P2 for a well measurement, because different amounts of air are sealed within the gauge in each case, the internal pressure at. or corrected to, calibration temperature Tr will he different by where all temperatures and pressures are absolute. The calibration temperature is used, and not the well measurement temperature, because the usual temperature correction reduces the well measurements to calibration temperature. The correction term as calculated by the above equation is separate from. and in addition to, the usual temperature correction. Example: T, = 540°R, sealing temperature at calibration P, = 14.7 psia, sealing pressure at calibration T2 = 460°R, sealing temperature at well P2 = 14.7 psia, sealing pressure at well Tr = 660°R, calibration temperature AP = 660 [14.7/460 — 14.7/540] = 3.1 psi While this error is small even under these somewhat maximal conditions, it nevertheless represents a practical situation which did occur, and which as a matter of fact gave rise to this note. Where AP is positive, as above, the correction is added to the measured pressure; where negative, subtracted from the measured pressure. This correction should also be considered in successive calibration runs where the gauge, for example, may be warm from a previous calibration at an elevated temperature. ERROR NO. 2 Where a small quantity of moisture (liquid water) is sealed within the gauge at atmospheric conditions, the increased vapor pressure of the water at higher well or calibration temperatures will cause an increase in internal pressure. This moisture will come presumably from condensation within the gauge following temperature changes, from moisture on the operator's hands, and from atmospheric moisture (rain, mist, fog, etc.). Calculation shows that approximately 0.2 cc of water (three to four drops) is sufficient to saturate the air within an Amerada RPG-3 Gauge at 160°F, at which temperature the vapor pressure of water is about 5 psia. As the vaporization occurs in a sealed volume, the increase in internal pressure will be in excess of this 5 psi. At higher temperatures the pressures will be higher; however more water will be required to saturate the air within the gauge. Some experimental work was carried out with an Amerada RPG-3 Gauge at 200°F fitted with a 1,000 psi element, both with a dry recording chamber and with a small amount of water added. The results directly proved the existence of the error due to the presence of moisture, and, it is felt, indirectly, due to the differences in sealing temperatures and pressures, as both effects may be ascribed simply to an increase in the moles of gas within the recording chamber. SUMMARY In precision measurements the error introduced by sealing the gauge during a well test at a different temperature and pressure from that of calibration may be corrected for by using the equation presented, or it may be prevented by taking care always to seal the gauge at near calibration conditions. The error introduced by sealing moisture in the gauge may be prevented by taking care to keep moisture out of the gauge, or by removing the moisture by either warming or evacuating the gauge. Both of these errors are independent of the range of pressure measurement and the type of gauge, and are in addition to the usual temperature correction. ACKNOWLEDGMENT Appreciation is expressed to W. B. Kendall, Geophysical Research Corp., Tulsa, Okla., who pointed out the error from differences in sealing temperatures during some winter work in Canada. ***

Jan 1, 1956

By A. S. Venkatadri, H. B. Bell

The equilibrium sulfur distribution between molten iron and Ca0-Mg0-Al203 slags containing iron oxide was investigated at 1550°C. The results were used to derive the iron oxide activities at low iron oxide concentrations in the slag by combining the sulfide capacity data obtained from gas-slag work with the free energies of both the sulfur solution in iron and the iron oxide formation in slag. The derived ferrous oxide activities were compared with values based on Tem-kin's kin's and Flood's ionic models. One difficulty in using these models is that the nature of the aluminate ion in slag is uncertain. Nevertheless, such indirect methods, in particular, those described in the present paper, are of value because of the difficulty of measuring small amounts of oxygen in liquid iron in equilibrium with slag. It is shown that these methods confirm the consistency of thermodynamics data on liquid iron and slags. It is well established that decreasing the iron oxide activity in the slag increases the desulfurization of molten iron at constant slag basicity. This effect is most pronounced at the very low iron oxide activities, characteristic of blast furnace slags. Yet a precise quantitative determination of the significance of low iron oxide contents in slag in blast furnace desulfuri-zation is not possible for the following reasons: a) difficulty of separation of iron "shots" from the slag, and b) errors in chemical analysis of small amounts of iron oxide in slags. In view of these obstacles, one must resort to indirect methods of calculating iron oxide activities. EXPERIMENTAL TECHNIQUE The apparatus for providing the sulfur equilibrium data has been described previously1 and was similar to that used by ell' in connection with the study of slag-metal manganese equilibrium. The procedure consisted of: a) melting about 50 g of Armco iron in a magnesia crucible in a platinum furnace, b) adding a mixture of about 15 g of lime-alumina slag and varying amounts of Fe2O3 and CaS, and c) maintaining the temperature at 1550°C for more than an hour in an atmosphere of argon to enable the sulfur equilibrium to be attained. Several melts were made using lime-alumina slags with basic composition 55, 50, and 45 pct lime. During the experiment the temperature was controlled manually using a Pt/10 pet Rh-Pt thermocouple. After the experiment, the Power was shut off and the flow rate of argon was increased to freeze the melt as quickly as possible. The analysis of sulfur in the metal was carried out by the oxygen combustion method3 using uniform drillings from the top and bottom of the metal button. After crushing and grinding and removal of any iron particles with the aid of a hand magnet, the slag was analyzed for sulfur by the CO2 combustion method.4 The E.D.T.A. method was employed for the analysis of lime5,6 and magnesia,= the ceric sulfate method7 for the analysis of slag iron oxide, and the perchloric acid dehydration method5 for the analysis of silica. The remaining amount was taken to be Al2O3 precipitation with ammonium hydroxide in several preliminary melts had confirmed the propriety of using this simple procedure. RESULTS The activity of iron oxide in binary, ternary, and more complex slags has been the object of numerous investigations, and the two experimental methods for its determination are: 1) Equilibrating the metal with the slag in question and measuring the oxygen content of the metal. The ferrous oxide activity is then given by aFeO L%OJSat where [%0]sat is the oxygen content of the metal in equilibrium with pure iron oxide slag. This method was used by Chipman et al.8,9 2) Equilibrating the slag in iron crucibles with known partial pressures of H2/H2O or CO/CO2 mix-tures.10-12 This method is limited to temperatures between 1265" and 1500°C. The very low oxygen content of the melts in this investigation made it impossible to derive the ferrous oxide activity by the first of these methods. Therefore, the iron oxide activities were computed by means of: Sulfide capacity data from the gas-slag work" Temkin's concept14 Flood's approach15 a FeO from Sulfide Capacity. The method of calculating the aFeO involves the sulfide capacity of the slag (c,), the sulfur distribution coefficient (Ls), the free energy of dissolution of sulfur in iron, and the free energy of formation of iron oxide in the slag. Bell and Kalyanram13 have investigated the sulfur absorption characteristics of lime-alumina slags containing magnesia by the Carter-Macfarlane method16 (based on comparing the sulfide capacity of the slag in question with that of a standard slag of unit lime activity) and have derived lime activity values. The relation between sulfide capacity and their lime activity a'CaO is given by: Cs= 3—: Xa'CaO at 1500°C

Jan 1, 1970

By W. O. Philbrook, K. M. Goldman, G. Derge

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951

By David J. Mack

THE structures and properties of the copper-aluminum alloys have been the subject of much study since the classic investigation of Carpenter and Edwards1 focused attention on the engineering utility of these alloys. It was recognized at an early date that the metallographic structures developed in the aluminum bronzes were similar to those developed in steels, both in the annealed and the rapidly cooled state. Most investigators have been concerned with the acicular, martensitic-like structure formed from the ß solid solution upon rapid quenching; the transformation of the ß under equilibrium cooling to a lamellar eutectoid having been relatively neglected. With the introduction in 1930 by Davenport and Bain2 of the isothermal transformation technique for studying eutectoidal decompositions, a new field was opened. Although an enormous amount of work has since been done on the isothermal transformation of steel, study of structurally analogous systems has been almost totally overlooked. The outstanding exception was the prize-winning paper† of Smith and Lindlief3 who investigated the decomposition of the ß phase in copper-aluminum alloys by isothermal methods. This was followed in 1934 by Wasserman's reviews of available information on analogous transformations in eutectoid alloys. Since that time no comprehensive study of isothermally transformed eutectoids analogous to steel has appeared, although many valuable contributions have been made to an understanding of the structures developed in such systems. Important papers have been published by Kurdjumow, Gridnew and co-workers, 5-17 Obinata,18,19 Greninger,20,21 and others .22.28 The work to be described in this paper was an out-growth of preliminary studies on the isothermal transformation of a eutectoid aluminum bronze, after it became apparent that the alloy under study was reacting somewhat differently than the similar alloy used by Smith and Lindlief. PRELIMINARY EXPERIMENTS The material used in this study was a high purity aluminum bronze especially prepared by Ampco Metal, Inc. It analyzed: Copper-88.o7 pct, Aluminum-11.89 Oct, Iron-0.02 pct, Manganese-0.01 pct, Others-Balance. Although some disagreement exists on the exact composition of the eutectoid, this alloy was believed to be of essentially eutectoid composition even though some pro-eutectoid* delta particles existed in the microstructure of furnace cooled specimens. Specimens transformed isothermally at temperatures slightly below the eutectoid showed relatively large amounts of pre-eutectoid delta, but as will be shown later, this results

Jan 1, 1947

By Oscar A. Glaeser

THE mine and plant of the United Verde Copper Co., located in Yav-api County, at Jerome, Arizona, have been described in various technical publications and, therefore, a brief outline of its essential features will suffice. The orebodies are of the schist replacement type, the main sulfide mass being a large lens-shaped body approximately 7 acres in cross-sectional area. In general, the mineralization is found along the iron-schist contact, with the orebodies extending about 1000 ft. along this contact and varying from a few feet to 250 ft. in width. The mine is located on a mountain slope and has openings into it on three horizons, as follows: 1. Raises and ore passes open vertically into the shovel pit. These extend down to the 1000-ft. level, where they terminate as loading bins in the Hopewell adit. The main fan intake air shaft, which also extends vertically down to the 1000-ft. level, has its surface opening on the hillside at the extreme north end of the shovel pit, and the main mine air return exhausts through a raise at the extreme south end of the shovel pit. 2. The 500-ft. level adit. 3. The Hopewell adit on the 1000-ft. level. The mine has a vertical downward extent of 2000 ft. below the 1000-ft. level. Underground operations are carried on through two main shafts, both of which are wholly underground. Shaft 5 is the ore-hoisting shaft. It has three compartments and extends from the 800 to the 3150-ft. level. Shaft 6 is the service shaft, and is used for lowering and hoisting men and material. It has a large cage compartment and three smaller compartments for counterweights, ladderway, and pipe and power lines. This shaft extends from the 500 to the 2550-ft. level, and is now being extended to the 3000-ft. level. An air shaft for the downward movement of fresh air from the fan has been provided, and extends to the 2550-ft. level at this time. Work has been started to extend this air shaft to the 3000-ft. level. A return airway for vitiated mine air, in the form of raises and short connecting drifts, extends downward to the 2100-ft. level. The underground mining operations extend from the 300 to the 3000-ft. level. There are about 45 stopes in active operation on the 17 levels

Jan 1, 1929

By N. A. Gjostein

The self-diffusion coefficient D, for a surface near the (100) plane in copper was determined by means of the Mullins theory of thermal grooving, and was found to obey the Arrhenius relationship, and Do = 6.5 x 10' sq cm per sec. Suppression of surface diffusion by chemisorbed impurities encounters difliculties as a satisfactory explanation for the large Q, and Do. Instead, a model is presented which indicates that Q,, as determined by a mass-transport technique, may involve both the energy needed to form an adsorbed atom from a ledge in the surface as well as that for the movement of the adsorbed atom.; LITERATURE reviews1-3 indicate that the mechanism of self-diffusion on metal surfaces is not clearly understood. The lack of experimental data on the temperature variation of the surface self-diffusion coefficient DJ has contributed greatly to this situation. Radioactive tracer techniques4-rn have been used to measure Ds, but for many years only Nicker-son and Parker8 had determined (for polycrystalline silver) an activation energy B, and a frequency factor Do for the surface self-diffusion process. Even in this case, a mechanism could not be clearly inferred because it was suspeted7 that a contribution from volume diffusion was not taken into account by the investigators. Some later work by Li and parkere on polycrystalline gold, in which they obtained essentially the same results as for silver and in which volume diffusion could be accounted for, seems to invalidate this criticism. In 1957, Mullins10'11 developed the theory for the thermal grooving process. This advance has opened a new and promising technique for measuring the surface self-diffusion coefficient Ds. Recognizing that a thermal groove may form by several different mass transport processes, Mullins first consideredlo the cases where a) the groove forms by evaporation and condensation or b) by diffusion along the groove surface, in either case, in a system where a metal surface is in contact with only its dilute vapor phase. In a later paper," he extended the treatment to cases where the groove forms by volume diffusion into c) the solid phase or d) by mass transport through a passive gaseous phase at 1 atm pressure. The time dependence of the groove dimensions and the shape of the groove profiles predicted by Mullins' treat-

Jan 1, 1962

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days 'steel' was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days 'steel' was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By R. F. Mehl, J. K. Stanley

THE recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are employed.1 Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystallization is not a heterogeneous reaction .within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress.4,5? The theory of recrystallization is not in advanced state; if recrystallization data were obtained, in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert measurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now

Jan 1, 1942

By C. H. Mathewson, Robert Maddin, W. R. Hibbard

A SATISFACTORY mathematical relationship between shear, elongation and change of orientation in the axial straining of a single crystalline rod or wire may be based on a simple model in which blocks, representing glide lamellae, glide over one another and rotate so as to maintain the original fixed position of the axis as the wire elongates.1 Obviously such a model gives no information concerning strain-hardening or the atomic adjustments at the sliding surfaces and their influence on the internal structure of the blocks. Moreover such an operation could be conducted with rigid blocks only by using self-aligning grips or a flexible attachment which would permit the adjacent blocks to freely assume their changing orientations. There are many unsolved problems (see Andrade2) concerning the manner in which nature departs from the simple model in permitting the essentials of slip, rotation and elongation to occur along with strain-hardening and the appearance of glide lamellae of various dimensions and special characteristics, not fully appreciated at the present time. This paper describes part of an extensive investigation on the development and characteristics of glide ellipses in single crystalline alpha brass rods and is especially concerned with the observation of cross-slip in crystals oriented wholly within the range of slip on a single system according to the generalizations first presented by Taylor and Elam in 1923.3 EXPERIMENTAL PROCEDURE Half inch rods of alpha brass (nominally 70 pct Cu, 30 pct Zn) * were converted into single crystals by melting and gradual solidification in a graphite mold according to the Bridgman method.' In order to remove any coring, the crystals were homogenized at 800°C for 16 hr and tested by etching with a 50 pct nitric acid solution. The back-reflection Laue technique as described by Greninger5 was used for determining the orientations of the crystals. Standard stereographic operations were employed to locate the specimen axis in a triangle of the Taylor and Elam3 projection so that the slip plane and direction could be predicted. The lineage structure reported by Buerger6 was present in the crystals used in this investigation. However, only crystals were used in which the internal differences in orientation did not exceed two degrees. Very little is known concerning the effect of the presence of a lineage structure on the detailed mechanism of plastic deformation.

Jan 1, 1948

By F. J. Martin, W. G. Hubler

The Beattie mine is at about the center of Duparquet township in the Province of Quebec, Canada. It is 22 miles northwest of the town of Noranda. The elevation is approximately 1200 ft. above sea level. This locality, long considered a favorable one from the geological point of view, has been prospected for over 20 years, but no discoveries of economic importance were made until the present orebody was found by John Beattie in 1930. The specific gravity of the ore is 2.77. The gold occurs in intimate association with the sulfides, pyrite and arsenopyrite, which in turn are very finely disseminated in a silicified porphyry. The bulk of the gold is associated with the pyrite, only a small proportion being with the arsenopyrite. There are small amounts of magnetite, ilmenite and chalcopyrite present in the ore. There is also some hematite in the ore that is mined from near the surface in the open pit. Metallurgical Problems and Methods or Attack 1. The ore is extremely hard and resistant to grinding. 2. The sulfide minerals are finely disseminated in the gangue. 3. The gold, in turn, is so intimately associated with the sulfides that grinding to even 5 microns will not release all of the values for cyanidation. 4. It is necessary to make a high ratio of concentration in order to obtain a product sufficiently high in gold to meet high shipping and treatment charges. Hardness of the Ore.—Owing to the extreme resistance of the ore to grinding, it was recognized that grinding costs would be high. Microscopic tests showed that grinding to 95 per cent minus 325 mesh would be necessary to liberate a sufficient amount of the values in order to obtain a tailing assaying 0.02 oz. gold per ton, which is considered to have the economical minimum gold content that can be obtained. It is not feasible to grind this hard low-grade ore (0.18 to 0.20 oz.) to 95 per cent minus 325 mesh, so it was necessary to overcome the problem in another way. The following method was decided upon: (1) Fine crushing to minus 1/4 in.; (2) relatively coarse primary grinding; flotation of low-grade concentrates in the primary and rougher circuits and discarding the

Jan 1, 1935

By D. M. Blacknall, N. N. Winogradoff, E. W. Williams

Low-temperature measurements of photolumines-cence were used to evaluate the progvess in materials development. Variation of the impurity type, impurity concentration, and method of growth were used to clarify the chemical origin of defects in GaAs. Melt-g~ozun, epitaxial vapor-, and solution-grown samples were studied. A comparison of measurements at 77" and 20°K shows that more defects can be observed at the lower temperature. Th'vee residual defects were identified in relatively pure GaAs. These were: silicon, copper, and a gallium vacancy-donor complex. Solution growth from a gallium solution inhibits the formation of the latter two. Eleven defects were studied and the "optical" activation energy of some of these, namely, silicon, cobalt, and chromium, has not been reported in the literature before. THE discovery of the injection laser in 1962 prompted extensive measurements of the photoluminescence of GaAs. The measurements were made at 77°K on GaAs doped with shallow impurities at various doping levels and compared with electroluminescence1'2 and absorp- tion data.374 In addition, lower-temperature studies were made on relatively pure GaAS' and on GaAs doped with oxygen,5'" manganese,' and copper.' The observation of defects* in GaAs with photolu- *The word "defects" ~efers to both chemical impurities and native defects. minescence at low temperatures makes photolu mines-cence an invaluable tool in evaluating the progress in materials development. The only previous evaluation was done at 77°K when solution-grown and melt-grown GaAs were compared.O No identification of defects was made but it was shown that some of the deep-level luminescence seen in melt-grown GaAs was absent in solution-grown GaAs. The present work extends the comparison of preparation techniques to lower temperatures and to a study of epitaxial vapor-grown GaAs. It is particularly valuable for thin epitaxial layers since they cannot be analyzed by conventional analytical techniques. In addition, by varying the impurity type and impurity concentration the chemical origin and nature of defects in GaAs was demonstrated. Eleven defects were studied in all. Three of the defects were identified as residual defects which often contaminate GaAs prepared from the melt and the vapor. Only one such defect was observed in GaAs grown from a gallium solution and this was identified as silicon.

Jan 1, 1968