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By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By N. S. Stoloff, R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-Co and Fe- V alloys containing up to 25 pct solute have been studied in the temperature range 25° to - 196°C. The microyield stress is independent of temperature for all alloys studied, while the temperature dependence of the ordinary yield stress is large and comparable to that for unalloyed iron. An alloy-softening phenomenon is observed for many alloys relative to unalloyed iron, and appears to be a consequence of removal of inter-stitials from solution and their subsequent agglomeration. The ductile to brittle transition temperature is increased markedly by both cobalt and vanadium. Transmission electron microscopy observations reveal that cross slip and cell formation are restricted with increasing solute, which can account for many aspects of yielding and fracture behavior. IRON and other metals of bcc structure slip on many planes of the (111) zone at moderate and elevated temperatures, giving rise to wavy glide. At low temperatures, however, there is a tendency for slip to be restricted to planes of only one or two crystallographic types; in the case of Fe-Si alloys for example, (110) glide predominates, giving rise to planar slip bands."' Restriction of cross slip at low temperatures in iron has been linked by Brown and Ekvall3 to increased strain hardening in the preyield microstrain region, leading to an apparently large temperature dependence of the yield stress. Support for this view has been provided by Lawley and Gaigher4 from a transmission electron microscope study of molybdenum. They concluded that dislocations at lower temperatures, by virtue of their inability to change planes readily, are unable to interact and annihilate, leading to an increase in internal stress and work-hardening capacity. Restriction of cross slip at low temperatures has also been suggested to be an important factor in determining the ductile to brittle transition of single-phase solids, including metals of bcc structure.5 It is pertinent to note that most solute elements tend to raise the ductile to brittle transition temperature of poly crystalline ferrite,6,7 although in some cases, e.g., Fe-Cr7 and Fe-Al,8 the dilute alloys may actually yield at lower stresses than unalloyed iron. It appears, therefore, that solute elements may have an effect analogous to lowering the test temperature with regard to restricting cross glide. Such an effect has indeed been observed in the ionic alloy system KCl-KBr,9 in which bromine atoms, although causing little misfit and consequently little effect on the yield stress of KC1, have a pronounced effect in restricting wavy glide and inducing brittleness. The purpose of the present investigation was to determine the effects of selected solute atoms on the yield stress and fracture behavior of iron, and to elucidate in turn how the slip character was related to these properties. Since it is known that interstitial atoms exert a strong influence on the mechanical behavior of iron, the solute elements chosen for study were vanadium, which reacts strong with interstitials,10 and cobalt, which does not form highly stable interstitial compounds." EXPERIMENTAL PROCEDURE Four-pound ingots of each of the following alloys were vacuum-melted in zirconia crucibles: Fe-1, 5, 10, 25 at. pct Co, and Fe-1, 4, 10, 20 at. pct V. An ingot of unalloyed iron from the same original stock as that used for the alloy was remelted under similar conditions to eliminate variations in interstitial content arising from differing thermal histories. Chemical analyses of the iron, cobalt, and vanadium melt stock are listed in Table I. All ingots were rolled and swaged, commencing at 850°C, to 1/4-in.-diameter bar. The bars were then annealed at 850°C for 1 hr (except that the 10 and 20 pct V alloys were heated for 2 hr) to give a uniform equiaxed grain size of about 0.05 mm. Tensile samples of 0.125 in. diameter by 0.8 in. gage length were utilized for studies of the ductile to brittle transition. A second set of tensile samples were utilized for microstrain experiments in which strain sensitivity of 1 x 10"6 was achieved by a capacitance method.3 Cylindrical compression samples 0.250 in. diameter by 0.4 in. long also were prepared to study the influence of composition on the macroscopic yield stress, and for metallographic analyses of defor-

Jan 1, 1965

By M. E. Fine, A. A. Henderson

Investigation of the tensile properties of silver based aluminum alloy crystals was undertaken because it appeared attractive for studying strengthening effects due to Suzuki locking with minimum complication. Yield drops were observed in all alloy crystals (1, 2. 3. 4, and 6 at. pct Al) after strain aging at room temperature. No yield drops were found in similarly grown and tested silver crystals. The yield effects are attributed to Suzuki locking but the major portion of the solid solution strengthening to other mechanisms. INVESTIGATION of the tensile properties of single crystds of silver alloyed with aluminum was undertaken because it appeared to be a system in which segregation at stacking faults associated with partial dislocations1 would be the dominant factor in anchoring dislocations. First, silver and aluminum have closely similar atomic sizes and thus solute atom locking of a dislocation due to elastic interactions should be unimportant. Second, while both X-ray2 and thermodynamic3 investigations show short-range ordering in silver-based aluminum alloys, the degree of local order is quite small (X-ray measurements give v = EAB - 1/2(EAA + EBB) = - 0.025 ev and thermodynamic measurements give v r -0.007 ev) and should not be important in strengthening dilute alloys. Third, the stacking fault energy of silver is probably low (as indicated by the profusity of annealing twins) and is very likely diminished further and quite rapidly by aluminum additions since the A1-Ag phase diagram shows a stable hexagonal phase at only 25 at. pct Al. Also, a careful investigation in this laboratory4 has shown that the ratio of twin to normal grain boundaries in recrystallized alloys increases with aluminum content. Thus, with minimum complication from other factors, Ag-A1 alloys seem attractive for studying strengthening effects due to segregation at stacking faults of extended dislocations. EXPERIMENTAL METHOD Single crystals measuring 250 by 5 by 1.5 mm of pure Ag (99.99 pct) and Ag-A1 alloys (A1 of 99.999 pct purity) of nominal compositions* 1, 2, 3, 4, and 6 at. pct were grown in high-purity graphite molds from the melt under a dynamic vacuum (1 x l0-5 mm Hg). The technique consisted of moving a furnace having a hot zone (which melted about 0.5 cm of alloy) over a horizontal, evacuated quartz tube con- taining the mold and alloy at a rate of 3/8 in. per hr. Chemical analysis showed roughly the first inch of the crystal to be solute poor, the last inch solute rich; and the center section uniform in composition within the sensitivity of the analytical method (± 0.2 at. pct Al). The center section of the crystal was cut into five specimens. Gage lengths of reduced cross section, measuring from 1.5 to 2 cm in length, were mechanically introduced by means of jeweler&apos;s files and fine abrasive cloth with the crystal firmly held in polished steel guides. One-third of the cross section was then removed by etching and electro-polishing, the crystals were all subsequently annealed for several days at 850°C in a dynamic vacuum (<1 x 10-5 mm Hg) and furnace cooled to 200°C. The crystal orientations were determined using the usual back-reflection Laue technique. The Laue spots were sharp and of the same size as the incident beam. However, microscopic examination showed the crystals to contain substructures with subgrains of the order of a micron in diameter. The details of this substructure are presently under investigation. Tensile testing was done with a table model Instron using a cross-head speed of 0.002 in. per min. For testing at various temperatures the following media were used: 1) 415oK, hot ethylene glycol; 2) 296ºK, air, acetone, water; 3) 273ºK, ice water; 4) 258ºK, ethylene glycol "ice" in ethylene glycol; 5) 200°K, dry ice in acetone; 6) 77ºK, liquid nitrogen. EXPERIMENTAL RESULTS A) Yield Behavior—A portion of an interrupted stress-strain curve for a 6 at. pct A1 crystal of the indicated orientation tested at room temperature is shown in Fig. 1. Initially, at (a), there is a small, gradual yield drop of about 10 mg per sq mm2. However, on stopping the test, and aging for a few minutes at (b), a sharp yield drop is found. Aging for longer times at (c) and (dl results in larger yield drops (and larger AT&apos;S). At, defined in Fig. 1, is usually larger than the yield drop by about 20 pct; however, this increase in the lower yield is transient since extrapolations of the flow stress curves join as may be seen from Fig. 1. (Both Laue and low-angle scattering photographs revealed no evidence of precipitation in a strain-aged 6 at. pct A1 crystal.)

Jan 1, 1962

By G. M. Yocom

Blowing acid Bessemer converters with oxygen-steam produces steel of below 0.002 pct N2 content. This method of blowing, combined with a dephosphorizing treatment in the steel ladle, results in low-carbon steels of low nitrogen and low phosphorous (under 0.035 pet) contents, which has physical properties equivalent to open-hearth steels of similar analysis. Using a 50-50 mixture of oxygen and steam, the refinitzg rate is increased 25 pct over blowing with natural air, and scrap charge increased from 3 to 10 pet. Bottom life is normal with proper tuyere area and arrangements, fumes are decreased, yields increased, and hydrogen content is normal. THE acid Bessemer plant at the South Works of Wheeling Steel Corp., consists of two 15-ton bottom blown converters with a monthly capacity of 57,000 N.T. The product of the shop is skelp billets for continuous welded pipe and slabs for ordinary drawing and forming quality sheets. Approximately 50 pct of ingot production is regular Bessemer steel of natural Phos content and the remainder is a dephosphorized grade of steel made by a special treatment of the blown metal as it is poured into the steel ladle. The low Phos grade of steel has certain advantages over the higher Phos grade but since both grades were produced by blowing natural air, the N2 content was in the range of 0.015 pct which limited its application. In 1954 it was decided to explore the possibilities of blowing with a steam-oxygen mixture for the production of steel of both low N2 and low Phos contents. The necessary equipment was installed to operate one converter in this manner and early in 1955 an experimental run of 160 heats was made by blowing with a steam-oxygen blast and excluding natural air entirely. During this period the proper operating techniques were established, such as blast pressures, steam-oxygen mixtures, valves and instrumental control equipment, tuyere arrangement in the bottoms, blowing times and production rates, and a thorough study made of the final steel quality. Also during this experimental period the dephosphorizing practice was improved by the use of a tap hole below the lip of the vessel. This provided a clean separation of the acid converter slag and blown metal which made the dephosphorizing treatment more effective. The results of this experimental run dictated further development of this practice and a second run of 720 heats was made in 1957. The quality features and conversion cost results were in line with expectations and accordingly a 400-ton per day oxygen plant is now being installed. The plant is scheduled for completion in September of this year. This will provide sufficient oxygen to operate both vessels on steam-oxygen blast and delete natural air blowing entirely. The steel will then be below 0.002 pct N2 bar content and the dephosphorized grades will be between 0.015 and 0.040 pct Phos. STEAM-OXYGEN BLOWING The steam for the process is fed to the plant at 220 psig pressure through a 6-in. line. The high-purity oxygen is compressed to 200 psig and conducted through an 8-in. line. The oxygen from the main line is valved down to 100 psig and passed through a steam heated heat exchanger. The heat exchanger is regulated to supply oxygen at 300°F to the steam-oxygen mixing station. It is essential that the incoming oxygen be held at this temperature to avoid condensation of the steam with resulting excessive erosion of the clay tuyeres in the vessel bottom. Oxygen is admitted to the mixing chamber by a 6-in. hydraulically operated valve driven by the ratio control regulator on impulse from the flow of steam. Steam is admitted to the steam-oxygen mixture station through a 2 1/2-in. hydraulically driven valve. The ratio control regulator acts to increase or decrease oxygen input as the steam flow increases or decreases with changing positions of the Blower&apos;s control lever. The important point to note here is that steam flow always precedes the oxygen flow as a safety measure. The control valves have sufficient capacity to afford protection should blow pipe trouble develop. A 50-50 mixture for these 15-ton heats demands an oxygen flow of 3800 standard cu ft per min along with 317 lb of steam. The Blower&apos;s stations is provided with an indicating blast pressure gage, and indicating steam and oxygen flow meters. Signal and warning lights indicate the valve positions and line pressures. A control room at the real of the Blower&apos;s pulpit room houses the ratio control and pressure regulators, as well as the various meter bodies. The hand actuated wheels used to change the conditions are mounted on a panel on the front of the meter control house. The recording steam and oxygen meters used for totalizing and accounting purposes are also mounted on this panel.

Jan 1, 1962

By Brian F. Dyson

The surface tensions at 1550°C of some Fe-S alloys (in the range 0.008 to 0.052 wt pct S), Fe-Sn alloys (0.31 to 48.4 wt pct Sn), Fe-P alloys (0.038 to 2.38 wt pct P), Fe-Cu alloys (2.15 to 22.8 wt pct Cu), and Fe-1 pct C-S alloys (0.005 to 0.076 wt pct S) along with the surface tension of the base iron have been measured by the sessile-drop method. A mean value of 1754 dynes per cm was found for the surface tension of the base iron. Sulfur was found to be highly surface-active, the surface-tension results being in quantitative agreement with existing data. Tin and copper were found to be less surface-active than sulfur while phosphoms was completely nonsurface-active. The surface tensions of Fe-1 pct C-S alloys were found to be lower than those of the Fe-S alloys containing the same sulfur content. This was shown to be a mmzifestation of the increase in the thermodynamic activity of suZfur by carbon. It is only in recent years that attempts have been made to measure the surface tension of liquid iron of known high purity.1-3 Earlier measurements4-7 were made on liquid iron containing variable amounts of what are now known to be surface -active solutes. The exact value of the surface tension of liquid iron is still, however, open to some doubt. Halden and Kingery&apos; reported a value of 1720k 34 dynes per cm at 1570°C, Kozakevitch and Urbain8 gave 1790k 25 dynes per cm at 1550°C, while Van-Tszin-Tan et al. obtained a value of 1865k 37 dynes per cm at 1550°C. The first systematic investigation into the effect of controlled solute additions on the surface tension of iron was made by Halden and Kingery.&apos; They showed that sulfur and oxygen were highly surface-active, whereas nitrogen was only slightly active, and carbon inactive. A subsequent investigation by Kingery indicated that two other group-6B elements, selenium and tellurium, were also surface-active. This highly surface-active nature of sulfur and oxygen has recently been substantiated by Kozakevitch and Urbainla and Van-Tszin-Tan et al. l1 Kozakevitch and Urbainl2 have also conducted an experimental survey of the effects of a number of metals on the surface tension of liquid iron. Their surface-active nature was, in all cases, less than that of the group 6B elements. The present investigation was undertaken to study in more detail the surface tensions of dilute Fe-S alloys and to measure the surface tensions of binary alloys of iron containing phosphorus, copper, and tin. The effect of sulfur additions on the surface tension of Fe-1 pct C alloys was also determined. EXPERIMENTAL PROCEDURE The sessile-drop method was employed in the present investigation. An apparatus was built similar in principle to that described by Humenik and Kingery.lS It consisted of a horizontal silica tube, which could be evacuated to pressures less than 10-5 torr, with its central portion surrounded by a water jacket within which was a high-frequency coil. This generated heat in a tantalum susceptor placed inside the silica tube, which in turn radiated heat to the specimen mounted on a recrystallized alumina plaque. Temperatures were measured by an optical pyrometer and photographs of the molten drop were taken on a fixed-focus plate camera giving a magnification of X2. Surface-tension values were determined from the resultant drop using the method described by Baes and Kellogg.l4 The high vapor pressure of molten iron made it necessary to conduct all the experiments under a 1/4 atm of argon (greater than 99.995 pct purity). The analysis of the base iron used in the investigation is given in Table I. Each sample was approximately 3 g in weight and had a hemispherical base to ensure a uniform advancing contact angle on melting. The iron alloys were prepared individually in the sessile-drop apparatus by drilling a hole in the top of each sample and adding the required amount of solute, the drops being analyzed after the experiment. This method of preparation had the advantage of ensuring a consistent minimal contamination by oxygen due to refractory attack and also allowed surface tension to be measured at the same time. Every precaution was taken to ensure that the specimen was not contaminated by grease when it was introduced into the apparatus, the samples being cleaned in acid, dried in alcohol, and rinsed in petroleum ether. All handling was done with tweezers. Once the specimen had been placed inside the susceptor, the furnace was evacuated and the Sample leveled. The furnace was then degassed at approximately 1000"C before the argon was introduced. In every case the surface tension was determined at 1550" C.

Jan 1, 1963

By E. R. Russell, N. E. Richards

The current ejyiciency of aluminum cells was derived from the metal produced over a period of time and the theoretical faradaic yield. The difference in the actual amount of aluminum in the cathode at the beginning and end of the period must be determined. The weight of aluminum in the cathode was calculated from the dilution of an added quantity of impurity metal. Use of multiple indicator metals, copper, manganese, and titanium, demonstrated that the weight of aluminum in cells can be determined to within 1 pct with routine but careful chemical analyses. Over intervals of the order of 30 days, current efficiencies reliable to within 1 pct can be obtained. INVESTIGATIONS beginning with those of Pearson and waddington ,&apos; through the most recent published work of Georgievskii,9-11 illustrate the direct relationship between the composition of the anode gas and the applicability of analysis of anode gases to the control of alumina reduction cells. McMinn12 noted the lack of an independent method for measuring cell production efficiency over the short term. There is no doubt that changes in the current efficiency are immediately reflected in the composition of anode gases. However, the accuracy of faradaic yields calculated from gas analyses depends upon the degree of interaction between primary anode gas and Carbon.6 A conventional industrial practice of obtaining long-term current efficiency for production units from mass balances and quantity of electricity is generally insensitive to the impact of planned control of any one or more of the influential reduction cell parameters such as temperature, alumina concentration, and mean interelectrode distance. Consequently, there is a real need in the aluminum industry for a procedure to obtain the absolute cell current efficiency over a short term—10 to 30 days—both for the calibration of values obtained from gas analysis6 and for evaluating the effect of controlling specific parameters in the reduction process. The amount of aluminum produced may be determined by considering the cathode pool as a reduction of an impurity metal in aluminum. Analyses over a period will show a decreasing concentration of the impurity due to the accumulation of aluminum solvent. The increase in aluminum inferred from analyses is the amount produced by the cell during the period. Combining weights of the cell aluminum in the cathode at the beginning and end of a specific period, weights of aluminum tapped and the quantity of electricity passed during the interval will yield the current efficiency. Smart,I3 Lange;4 Rempel,15 Beletskii and Mashovets,16 and winkhaus17 have used dilution techniques to determine aluminum inventory in alumina reduction cells. A technique for determining the weight of aluminum in production cells by addition of small amounts of copper to the aluminum cathode was described by smart.13 The precision in values of the aluminum reservoir through dilution of copper in the cathode ranged from about 1 to 3 pct depending upon the quantity of copper added in the range 0.2 to 0.01 wt pct, respectively. Because the method appears so direct and apparently simple, one would not anticipate difficulties in application to industrial cells. The objective of this study was to resolve this problem associated with the trace metal dilution technique for determining the amount of aluminum in a cell. The approach in evaluating trace metal dilution as a basic factor in determining the weight of aluminum in the cell reservoir, and the absolute current efficiency of the Hall-Heroult cell, was to dilute more than one trace metal in the aluminum cathode so that we could discriminate among complications arising from physical mixing, the possibility of separation of intermetallic compounds, loss of the added elements, and chemical detection. EXPERIMENTAL METHODS These experiments are not complex but require standardized procedures. The technique involves addition of the trace metals to the cathode, knowing when these metals are homogeneously distributed in the liquid cathode, timing of the sampling, employing accurate and precise analytical methods, using reliable procedures for monitoring the amount of electricity passed through the cell, and accurate weighing of aluminum removed from the cell during the particular period. More accurate results might be obtained if the increment in concentration of the added indicator metals were of the order of 0.1 to 0.2 wt pct. The method must be applicable to production units and, hence, the contamination of the aluminum minimized. For this reason, the concentration of trace metals in the cathode was kept below 0.07 wt pct and generally at 0.04 wt pct level. Trace quantities of copper, manganese, titanium, and silicon are already present in virgin aluminum and are suitable as additives from electrochemical and analytical points of view. Concentration of silicon is quite dependent upon the characteristics of the raw materials and was not used extensively in this work. Chemical Analyses. All instrumental analyses require calibration against an absolute technique such as a gravimetric, volumetric, or spectrophotometric method which represents the ultimate in sensitivity, precision, and accuracy. On review, the best methods for copper appeared to be optical absorption without

Jan 1, 1969

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.&apos; 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.&apos; 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 S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of silver and copper in dilute Ag-Cu-Sn alloys at 720°K have been determined using a liquid metal-solution calorieter. Values of the se2f-interaction coefficient n AgAghave been calculated at constant copper concentrations and n Cu Cuhas been determined at constant silver contents. The reliability of the experimental data is shown by the very good agreement between nCujAg and ij &$; these interaction coefficients have experimental values of -9100 and - 9590 cal per g-atom, respectively. Certain solution models are shown to be inadequate for prediction of solute interaction coefficients in dilute Ag-Cu-Sn alloys. In a previous publication&apos; the results of a thermody-namic study of dilute Ag-Au-Sn alloys were presented. The present work represents the continuation of a program to investigate dilute alloys of the noble metals with tin and in particular is concerned with solute interactions in the Ag-Cu-Sn system. By determination of the magnitude and sign of the various interaction coefficients in dilute alloys it is possible to gain some understanding of the different types of solute-solute and so lute-solvent bonding changes that occur as the solute concentrations are varied. Hence systematic studies of alloys with similar physical characteristics as regards size, structure, electronegativity, and so forth, of their components can contribute a great deal to present theoretical knowledge of solutions. The recent definition of an enthalpy interaction coefficient, 11, by Lupis and Elliott2 is of particular value in calorimetric studies such as the present one: where j and i are solutes and s is the solvent; Si is the relative partial molar enthalpy of component i and x represents the mole fraction of solute or solvent. Values of ?Hi can be obtained directly by solution calorimetry and data for n are thus easily determined, often with a high degree of accuracy. ?Hi is related to the relative partial molar enthalpy at infinite dilution, ?Hi and to the enthalpy interaction coefficients by the expression: ?Hi?Hi + X;nz+ ... [2] The aim of the present work was to determine the self-interaction coefficients n AgAgand 178: in alloys of different compositions and also to establish values for n Agcg| and ncuAg. Since it is a thermodynamic requirement (resulting from the Maxwell-type relationships which can be applied to partial molar properties) that nAgcu and ncuAg should be equal, a further aim of this study was to demonstrate the agreement between experiment and theory. EXPERIMENTAL A description of the liquid metal-solution calorimeter used in this research has already been published,3 and no further details of its construction and operation will therefore be given here. Copper supplied by the American Smelting and Refining Co. was indicated by them as being 99.999 pct pure, and the silver obtained from A. D. Mackay, Inc., was also quoted as being 99.999 pct pure. A solvent bath consisting of between 70 and 80 g of 99.99 pct pure Sn was used for each series of experimental drops. Its weight was accurately determined and the appropriate amounts of copper or silver were added to give alloys of the desired composition. Approximately 0.00125 g-atom additions were used for determinations of the heat of solution of silver in the bath, while, for copper, specimens consisting of approximately 0.0015 g-atom were used. The heat capacity of the bath was determined at regular intervals during a series of drops using tin or tungsten calibration samples. The heats of solution of silver and copper in pure tin were first determined as a function of their concentration in order to establish the self-interaction coefficients 7AgAg and ncucu Alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of copper were then used to study 17:: in alloys of different copper content, while alloys of the same mole fractions of silver were used to determine equivalent data for 178: at constant silver concentrations. The composition of the bath was held at the desired copper or silver concentration by making calculated additions of the appropriate solute throughout the experiment. From the limiting values of ?HAg in the constant copper content alloys it was possible to study ?HAg as a function of xCu and hence to determine 42:. A similar analysis of the re, values permitted calculation of nAgcu. Heat content and heat capacity data from Hultgren et al* were used to calculate heat of solution values from the measured heat effects at the experimental temperature of 720°K. RESULTS AND DISCUSSION Determinations of ?HAg. A preliminary investigation of the heat of solution of silver in pure tin at 720°K was first made in order to establish the value of nAgAg before additions of copper were made and also to compare the value of ?HOAg(l) with that obtained in the previous study of Ag-Au-Sn alloys.&apos; Then the heat of solution of silver in Cu-Sn alloys was investigated as a func-

Jan 1, 1970

By W. H. Porter, M. E. Wadsworth, J. R. Lewis, K. L. Leiter

The oxidation of Cu2S in oxygen and the sulfating of Cu2O in oxygen-sulfur dioxide atmospheres was carried out under a variety of conditions. The oxidation of Cu2S was found to be retarded by entrapment of SO, and O2, which stabilized internal sulfates for long periods of time. The course of the reaction was followed by measuring weight changes and also by SO, evolution. Sulfating of Cu2O was a maximum at ratios of SO, to O2 approximating maximum SO, production. At elevated temperatures SO, was found to increase the rate of oxidation of Cu2 O to CuO even though sulfates did not form. All sulfating reactions followed the parabolic rate law indicating diffusion. MANY studies of the roasting of copper sulfides have been reported in recent years. Diev et al.1 investigated the roasting of chalcocite (Cu2S) in air, and oxygen enriched air. Lewis et al.2 also studied the oxidation of natural and synthetic chalcocite in air and oxygen atmospheres and their studies indicated that the maximum formation of water soluble sulfates occurred at approximately 450oC. Ashcroft3 reported that oxide production during the roasting of chalcocite resulted only from secondary decomposition of sulfates which were formed as primary products. peretti4 refuted this claim by showing that a layer of Cu2O appeared directly adjacent to the Cu2S during roasting of cylindrical briquettes of cupric sulfide, CuS. The linear advance of the Cu2S-Cu2O interface was used as a measure of the kinetics of the roasting reaction. The reactions proposed were: 2 CuS—Cu2S + 1/2 S2 [4-1] 1/2 S2 + O24 SO2 [4-2] cuzs +3/2 O2 4 Cu2O + SO2 [4-3] cu2o + 1/2 O2—2 cuo [4-4] At temperatures above 663oC, CuO was the only final solid phase reported. Below 663" C increasing amounts of sulfate were found mixed with the CuO. McCabe and Morgan5 investigated the roasting of discs of synthetic chalcocite and reported the following sequence of products beginning at the sulfide surface: Cu2O, a mixture of Cu2O and CuSO4, Cum,, CuO . CuSO4, and CuO. The principal reactions were reported to be: Cu2S + 3/2 O2-Cu2O + SO2 [5-1] CU2O + 2 SO2 + 3/2 O2—2 CUSO4 [5-21 2 CUSO4— CUO . cum, + SO3 [ 5-31 cuo . cuso4—-2 cuo + SO, [ 5-41 Eq.15-11 supports the claim of Peretti, Eq. [4-31, that CuzO is formed directly from Cu2S rather than as a secondary product from a sulfate as suggested by Ashcroft. On the other hand CuO was found to form as a secondary product from the decomposition of copper sulfate and basic copper sulfate, Eqs. [5-31 and [5-41. The formation of sulfates was explained by McCabe and morgan5 to be a direct reaction of Cu2O with 0, and SO, or SO, at distinct regions in which the partial pressures of each were such as to form the sulfate. Thornhill and pidgeon6 roasted both natural and synthetic chalcocite grains in air at temperatures between 420" and 550° C. They found a dense primary oxidation layer in contact with the sulfide. A secondary layer of porous oxidation products was found to expand with roasting time. The oxide products were leached away and the remaining core was studied by X-ray diffraction. The X-ray patterns showed an increased conversion of chalcocite to digenite with time. Digenite,7 a defect structure of cuprous sulfide, occurs naturally as Cu,-,S where x = 0.12 to 0.45, with an average analysis of Cu, ,S. The mechanism of digenite formation was proposed as: Cu2S + oxygen—Cu1-8S + 0.1 Cu2O [6-1] Cuj.eS + oxygen—0.9 Cu2S + SO2 [6-2] It is apparent from the above studies that the oxidation of Cu2S, ultimately ending in CuO, may be divided into ihree general stages (all of which may occur simultaneously): 1) primary oxidation to Cu2O; 2) secondary sulfate formation; and 3) sulfate decomposition. Consequently reactions of O2 and SO, with Cu20 constitute important aspects of the roasting of chalcocite. Virtually no studies have been made regarding sulfating reactions involving Cu,O. Mills and Evans8 noted the effect of sulfur dioxide on the oxidation of copper at low temperatures and low SO, partial pressures. They reported a measurable increase in the oxidation rate of copper when SO2, was present. Interest in the Cu2O-CuO-0, system has been limited predominantly to misciblllty studies and determinations of heats of formation by

Jan 1, 1961

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p&apos;robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI&apos;U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts&apos; wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.&apos; This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d&apos;~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU&apos;~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By Emerson F. Heald

A systematic study was made of new and old data on chemical activities in Fe-Pt alloys at elevated ternperatuves. Experimental results may be expressed in terms of the excess free energy using Least-squares analysis of the data gave the following values for the constants: for the temperature range 1130° to 1350°C, and tentatively to 155O°C, B = -3.326564 and C = 0.221051; for the temperature range 650" to 850°C, B = -2.555690, C = 1.762735, and D =0.097196. In the study of iron-containing silicate systems, it is sometimes desirable to have a direct experimental measure of the activity of iron in the system. The well-known solubility of iron in platinum, often a headache in experimental work on iron compounds under reducing conditions, can be used to advantage in this respect. If the activity of iron in an Fe-Pt alloy in equilibrium with the silicate is known as a function of the composition of the alloy, chemical analysis of the alloy will give a knowledge of the activity of iron in all of the phases in the system. The present study was undertaken in order to elucidate the characteristics of Fe-Pt alloys as iron activity indicators. This work is intended to tie together some previous work, which may be summarized as follows. Larson and Chipman1 determined the activity of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with calcium oxide-iron oxide-silica melts of known iron activity. Compositions of the resulting alloys were determined by chemical analysis. A similar study was carried out by Taylor and ~uan,&apos; who worked at 1300°C. They brought the Fe-Pt alloys into equilibrium with iron oxide under conditions of known partial pressure of oxygen, and thus, from the work of Darken and ~urr~,~ conditions of known iron activity. Compositions were determined indirectly, by following the change in weight of the sample. Sundaresen et el* used the electromotive force of cells in which the alloy formed one electrode in order to measure the activity of iron in the alloy at 650" and 850°C. These temperatures were chosen to be above and below the first-order phase transition which takes place upon the ordering of Fe3Pt and the second-order transition which occurs upon the ordering of FePt3. EXPERIMENTAL 1) High Temperatures. The starting materials used were thin platinum foil, about 0.002 mm thick, and Fisher Certified reagent ferric oxide, Fez03, which had been heated for 24 hr at 1000°C. An intimate mixture of 80-mesh Fez03 and platinum platelets was placed in a thin platinum foil envelope. The latter was suspended from thin platinum wires in the hot zone of a vertical-tube, platinum-wound furnace of the type described by Muan and ~sborn.~ A capillary gas mixer similar to that used by Darken and Gurry3 was used to prepare a precisely known mixture of carbon dioxide and hydrogen, which was allowed to flow upward through the furnace tube. The partial pressure of oxygen in contact with the sample was thereby fixed at a value which was calculated from the charts prepared by porter? Temperatures were measured with a Pt-10 pct Rh-in-platinum thermocouple, which was calibrated using the melting points of gold (1062 .@C) and diopside, CaMgSizOB (1391.5"C). Temperature control was maintained to within i3"C with a Geophysical Laboratory proportional controller, using the furnace resistance as the sensing element. Samples were quenched by passing a small current through the platinum suspension wires, allowing the sample to drop into a bath of dibutyl phthalate at the bottom of the furnace tube. Prior to chemical analysis the samples were washed with acetone and dried. 2) Chemical Analysis. It proved possible, in almost all cases, to separate the Pt-Fe platelets physically from particles of iron oxide. The platelets were dissolved in a small volume of aqua regia, evaporated to dryness, and redissolved to 0.1 M HC1. In order to determine iron in the platinum alloy potentiometrically, it is necessary first to remove the platinum. A 10-cm column of Amberlite IR-120 cation exchange resin in the hydrogen form provided separation quickly and quantitatively: The mixture of iron and platinum in 0.1 M HC1 was added to the top of the column, and washed with about 100 ml of 0.1 M HC1. Under these conditions, the iron, principally in the form of cations such as FeC1" and FeCl;, is held quantitatively in the uppermost centimeter of the column. The platinum, in the form of anions such as PtC&- , is washed through without being adsorbed. After a qualitative test with stannous chloride indicated all of the platinum was removed, the iron was

Jan 1, 1968

By H. R. Page, A. E. Jr Lee

From the inception of zinc retorting on a commercial scale in the United States in 1890,&apos; the retort employed has undergone wide variations in its composition and manufacture, facilitating in part equally remarkable improvements in furnace capacities. The early day hand made clay retort was charged with carbonates or silicates or with coarse dead roasted concentrates mixed with a large proportion of charge fuel resulting in a relatively low zinc burden and fired 24 hr in direct coal fired furnaces. Its modern counterpart is fabricated in hydraulic presses from clay mixtures containing sizeable amounts of either silicon carbide or silica flour, charged with sintered flotation concentrates to more than three times the early day zinc burden and fired 24 to 48 hr in gas fired furnaces. This paper does not attempt to describe in detail the early day clay retort practice as it is well outlined in treatises by Ingalls,2 Lodin,3 Liehig,4 Hofman5 and others. A brief review of clay retort practice is presented together with a description of the major developments since 1912. Clay Retorts The Belgian type retort, both in the circular and elliptical forms, has been used almost exclusively. Typical dimensions of press made clay retorts around 1910 are shown in Table 1. Variations in these dimensions were used at different plants according to local conditions to a maximum inside diameter of 9 in. and inside length of 54 in. However, the effective heat penetration in a 24 hr firing cycle and the tendency of the retort to bend limited the retort size. Use of the elliptical vessel was an attempt to present a stronger cross-section resisting the tendency to bend and to increase the burden without increasing the depth of heat penetration. One exception to the 48-54 in. length was the 60 in. retort used as early as 1905 at Palmerton by means of supporting the last 12 in. at the butt end with a specially designed furnace back-wall. This backwall construction with the 60 in. retort had been developed and used at Bethlehem by G. G. Con-vers and A. B. DeSaulles. An attempt was made at Blende, Colo. to use even larger retorts of the Rhenish type based on European practice and requiring much higher furnace temperatures. Satisfactory plastic clays capable of withstanding these temperatures were not available, and the plant never operated successfully. PREPARATION OF BATCH Composition of the clay retort by weight was 40 to 50 pct raw clay and the balance "grog." Generally speaking the mix consisted of 7 parts plastic clay to 9 parts grog by volume. Principal source of the clay used was the Cheltenham vein—sometimes referred to as "St. Louis city clay." A typical analysis was A12O3-31.0 pct, SiO2-50.0 pct, Fe2O3-2.5 pct, MgO-0.3 pct, CaO-1.5 pct and loss on ignition 14.0 pct. At the smelter the clay was weathered whenever possible and then crushed to 0.08 in. or finer. Grog consisted of calcined adobies, cleaned retort scrap and cleaned refuse fire brick such as old furnace brick, blast furnace linings, and others. Saggers from ceramic plants and calcined flint clay were later used. The grog materials were ground to 0.12 m. or finer. Occasionally coke dust up to 10 pct of the mix was substituted for a part of the grog following European practice.² Particle size of the grog has a major influence on the retort properties—the larger the grain, the better can the retort withstand thermal shocks, resist bending at furnace temperatures and resist corrosion from slag; the smaller the grain, the lower the loss of zinc vapor through the retort walls. Grog forms the skeleton of the retort, and the clay shrinks around its grains to act as a binder. In the drying process, the grog has a stabilizing effect on the drying rate, decreasing shrinkage and giving up previously absorbed water to the surrounding clay to minimize the danger of cracking or checking.² Grog and clay were mixed through a horizontal pug mill with 10 to 20 pct water added, depending on whether the retort was to be formed by hand or mechanically, more water being required for the hand process. The batch or "mud" extruded from the pug mill was cut in convenient lengths for handling, stacked in piles or in special rooms, covered with wet burlap and allowed to "rot" or age from 1 to 8 weeks to increase plasticity. HAND MOLDING If the retort was to be molded by hand, the mud was repugged after the rotting period and given to the molders. Their molds consisted of 3 sheet iron or wood cylinders, each one third the retort length and defining the outer shape of the retort. Beginning with the bottom section, mud was placed in the form and tamped with a rammer

Jan 1, 1950

By H. F. Silliman, Daniel R. Hull, John R. Freeman

IN the normal operation of a brass-rolling mill, sheet and strip has, for the most part, been finished in comparatively thin gauges, involving a substantial amount of coldwork and a considerable number of anneals. This condition has been disturbed by the prep0nderance of cartridge brass, which is not rolled to thin gauges, and particularly by brass for artillery cartridge cases, on which the mill may finish its work at a thickness between 0.400 and 0.900 in. Obviously, the amount of rolling and the number of anneals to which such a product can be subjected are small compared with strip that is carried to a thickness of a few hundredths of an inch. As a result, critical examination into the internal condition of metal has been made on an extensive scale at a stage of manufacture that would not, in normal times, have been chosen for complete inspection. Under these conditions, a type of defect has been recognized that is not seen at thinner gauges. It might be more accurate to call it the appearance of a defect, since it refers to an apparently laminated, discontinuous structure, which, in fact, does not exist as such, and disappears after suitable treatment. For this reason it has been called a phantom lamination, which the authors consider an appropriate term. It is the purpose of this paper to describe the phenomenon and the conditions of its occurrence and, at least tentatively, to discuss its nature and cause. Great numbers of phantoms may be found in 2: 1 brass, either hot-rolled or cold-rolled. They are also found in 70-30 brass, sometimes when hot-rolled and generally when cold-rolled. It is not believed that phantoms are confined to these alloys but this paper is limited to them for the purpose of description. HOT-ROLLED 2:I BRASS For illustration, therefore, a typical cake of hot-rolled 2: 1 brass has been chosen. This was rolled to a slab 7/8 in. thick, from a casting 5 in. thick by 24 in. wide by 18 in. high, which was believed to have been sound. After hot-rolling and cooling, the slab was sheared and a portion of such a shear cut is shown in Fig. 1. It would be difficult to convince anyone viewing this specimen that the metal was not unsound. The impression would be confirmed by the appearance of a tensile break, as shown in Fig. 2. This is an ordinary tensile-test piece from metal just described. Although there was nothing in its tensile strength or elongation that suggested unsoundness, it appeared run through with pipes and laminations. To question the reality of such a condition would imply questioning the obvious. But, considering the history of the metal, it w0uld be difficult to believe that it could be so bad as it appeared. It seemed reasonable, though, that if the defects were what they appeared to be, they could be traced back from the sheared or broken face.

Jan 1, 1945

By W. J. Millard

It is well known that the excellent mica from Brazil played a most vital role in World War 11. Increased production from Brazil was necessary and with the assent of the Brazilian Government engineers from the united&apos; States went down to study the problem. One of the means advocated by a former Chief of Metals and Minerals Branch of the Board of Economic Warfare, Mr. Carl Schwegler, was the use of stripping machinery. On a pegmatite dike favorable for stripping, a small number of miners could produce as much mica per day as an underground mine employing many times the same number of men. Type of Deposit Favorable The most favorable type of pegmatite for stripping is that which lies more or less parallel to the surface of the slope of a hill. Pegmatite dikes that cut directly into a hill are not suitable for stripping except where a long outcrop extends along the slope. Then just the outcrop could be stripped to some advantage. The ratio at no time should be greater than 1: 3; i.e., I cu. m. of pegmatite to 3 cu. m. of waste, unless the pegmatite was extremely rich throughout the dike. The Economics of Stripping When a mineral is badly needed to win a war, not too much heed can be paid to costs. The object is to produce rapidly and in quantity. Again, a deposit containing a superior grade of mica may be worked although the pegmatite is more costly to work than another deposit containing a considerably greater amount of poor-grade mica. For example: one deposit may have a little mica that will run 11 per cent good stain and better when trimmed and contain 2 kg, of crude mica per cubic meter of pegmatite, while another may run 0.2 per cent of good stain and better, and have a mica content of 10 kg. per cubic meter. A number of stripping projects were found in the vicinity of Raul Soares, Minas Gerais. These were sampled in the various old workings by cutting out a cubic meter of pegmatite and saving the usable mica. Because of the proximity to the surface of most stripping projects, about 34 per cent only of the mica is good for trimming. The other 66 per cent is too badly weathered to be of use. In Table I are given data collected on five properties near Raul Soares. In Table I, "value per cubic meter of pegmatite" means the value of the qualified mica obtainable. This does not include the half trimmed and splittings. By "value per cubic meter of matter" is meant the value of the qualified mica per cubic meter of material excavated; i.e. both waste and pegmatite. This is the figure that should be used to determine whether the operation will be profitable or not, as the cost of stripping is about $0.14 per cubic meter. With new machinery not subject to breakdowns, the cost per cubic meter should be around $0.10 to $0.15. To this should be

Jan 1, 1948

By W. J. Millard

It is well known that the excellent mica from Brazil played a most vital role in World War 11. Increased production from Brazil was necessary and with the assent of the Brazilian Government engineers from the united&apos; States went down to study the problem. One of the means advocated by a former Chief of Metals and Minerals Branch of the Board of Economic Warfare, Mr. Carl Schwegler, was the use of stripping machinery. On a pegmatite dike favorable for stripping, a small number of miners could produce as much mica per day as an underground mine employing many times the same number of men. Type of Deposit Favorable The most favorable type of pegmatite for stripping is that which lies more or less parallel to the surface of the slope of a hill. Pegmatite dikes that cut directly into a hill are not suitable for stripping except where a long outcrop extends along the slope. Then just the outcrop could be stripped to some advantage. The ratio at no time should be greater than 1: 3; i.e., I cu. m. of pegmatite to 3 cu. m. of waste, unless the pegmatite was extremely rich throughout the dike. The Economics of Stripping When a mineral is badly needed to win a war, not too much heed can be paid to costs. The object is to produce rapidly and in quantity. Again, a deposit containing a superior grade of mica may be worked although the pegmatite is more costly to work than another deposit containing a considerably greater amount of poor-grade mica. For example: one deposit may have a little mica that will run 11 per cent good stain and better when trimmed and contain 2 kg, of crude mica per cubic meter of pegmatite, while another may run 0.2 per cent of good stain and better, and have a mica content of 10 kg. per cubic meter. A number of stripping projects were found in the vicinity of Raul Soares, Minas Gerais. These were sampled in the various old workings by cutting out a cubic meter of pegmatite and saving the usable mica. Because of the proximity to the surface of most stripping projects, about 34 per cent only of the mica is good for trimming. The other 66 per cent is too badly weathered to be of use. In Table I are given data collected on five properties near Raul Soares. In Table I, "value per cubic meter of pegmatite" means the value of the qualified mica obtainable. This does not include the half trimmed and splittings. By "value per cubic meter of matter" is meant the value of the qualified mica per cubic meter of material excavated; i.e. both waste and pegmatite. This is the figure that should be used to determine whether the operation will be profitable or not, as the cost of stripping is about $0.14 per cubic meter. With new machinery not subject to breakdowns, the cost per cubic meter should be around $0.10 to $0.15. To this should be

Jan 1, 1948

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure&apos; which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies&apos; have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen&apos; determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By A. M. Gaudin, C. S. Chang

IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.1-4 The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods.5-6 In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba140 to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,4 were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand picked quartz, washed free of stains, were reduced in size to -20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This -200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then&apos; was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn,, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.7 The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74 micron quartz particles, using a surface factor of 1.96,8 is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1952

By V. A. Phillips, M. Safdar Ali

The tensile properties of Cu-0.20 pct Al, Cu-0.45 pct Mg, Cu-0.27 pct Cr, and Cu-0.22 pct Be solid-solution alloys were studied at -196°, 18°, 2509 and 500°C on wires internally oxidized at 900°and 1000°C. Internal oxidation produced marked increases in yield strength relative to pure copper, particularly at low temperature. The yield strength decreased with increase in temperature to a much greater extent than predicted by current theories of dispersion hardening. The strengthening effect of internal oxidation persisted throughout the entire stress-strain curve, but since a marked loss of ductility occurred at all test temperatures, only modest increases in tensile strength were realized. INTERNAL oxidation involves the preferential oxidation of a baser solute in a relatively noble solvent by diffusion of oxygen into the solid. Since the process is diffusion controlled, it is expedient to carry it out at a high temperature often approaching the melting point. The amount of solute is limited and the oxidation conditions adjusted so that oxygen diffuses inwards to meet the solute causing reaction to progress inwards and form subscale instead of only sur face scale. The reaction can be made to occur throughout the thickness of thin material producing a fine dispersion of oxide inside the metal. C. S. Smith1"3 appears to have been the first to recognize the true nature of the process of internal oxidation. Although extensive kinetic and metal-lographic studies followed by Rhines and coworkers,4-5 Chaston7 andMeijering and Druyvesteyn8 working independently were the first to report hardening effects due to internal oxidation. These results prompted detailed studies of the effects of internal oxidation on the hardness, tensile, creep, and fatigue properties of a number of alloys by G. C. Smith and coworkers9-12 in England, on hardness by Gottardi13 in Italy, and on hardness and tensile properties by wood14 in the U.S.A. Publications dealing with other aspects of internal oxidation will not be reviewed here. Internal oxidation of solutes having a high affinity for oxygen provides a means of obtaining very fine dispersions stable in a suitable atmosphere at temperatures well above those at which most age harden ing precipitates coalesce. The process therefore offers a method of producing thin sheet and wire of possibly outstanding creep resistance. The size limitation might be overcome by internally oxidizing porous powder compacts made from alloy powder before final sintering. PREPARATION OF ALLOYS The alloy ingots, which were approximately 5 1/2 in. long by 1 in. diam, were made up in a high-frequency furnace, using as raw materials OFHC copper, 99.99 + pct Al, high-purity magnesium, and master alloys of Cu-4.19 pct Be and Cu-10 pct Cr. The alloys containing aluminum and magnesium were melted ii closed high-purity graphite crucibles and solidified in the crucible which was lowered partly Out of the coil to give a hot-top effect. The alloys containing beryllium and chromium were made by melting in vacuo in alumina-lined sillimanite crucibles. The magnesium, chromium, and beryllium

Jan 1, 1960

By R. A. Stauffer

The chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll&apos;s and Dr. Schlecten&apos;s recent paper1 has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000ºC in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating-to about 1000ºC in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. The Replacement of Li2O in Spodumene A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide Present in the Ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh&apos; Analysis of the spodumene was as follows: PCT SiO2......................... 62.7 Al2O3........................ 29.9 Li2o......................... 4.9 Na2O........................ 0.89 CaO......................... 0.75 MgO........................ 0.49 K2O......................... 0.44 Lime (cp —200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000ºC in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1949