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By M. L. Fuller

IN connection with an investigation in this laboratory on the high-zinc side of the copper-zinc system, it was observed that well developed segre-gate structures of the Widmanstätten type were formed when a secondary phase precipitated from the solid solution of copper in zinc. This paper presents an analysis of the crystallographic relationship between the segregate and the solid solution matrix. The data to be presented are an interesting addition to the literature on segregate structures in that the plane of segregation is one of the less densely populated planes. In agreement with the generalization of C. H. Mathewson and D. W. Smith1 the plane of segregation in the matrix con-tains the direction of closest atomic packing of the lattice. Furthermore, the matrix and the segregate are both hexagonal close-packed, which has not been reported hitherto in the literature.2 The increasing com-mercial importance of zinc alloys containing copper makes this funda-mental study of value to the metallography of zinc alloys.

Jan 1, 1933

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By R. W. Cahn, C. D. Graham

The rate of growth of a single grain growing into a strained aluminum single crystal, measured by the conventional heat-cool-etch technique, is shown to decrease with time at temperature. The growth rate measured by means of X-rays, with the sample continuously at temperature, is found to be linear. Evidence is presented to show that the decreasing growth rate obtained by the conventional technique is due to abnormal recovery in the strained grain, and that the recovery in turn results from the heating and cooling cycles, rather than from the effects of etching. The experimental apparatus is described in an appendix. FREQUENTLY, the rate of grain boundary motion during recrystallization is determined by heating a sample to a known temperature for a given time, cooling to room temperature, and etching to reveal the boundary position. The cycle of operations is repeated as many times as necessary to establish the rate of boundary motion. Although this heat-cool-etch technique has been used by a number of workers over a period of many years,'-!' other investigators have encountered difficulty with the method."'. " They have attributed the erratic results to the effects of repeated heating and cooling, or of etching, or both, and have adopted an alternative experimental procedure in which a number of identical samples are employed, each sample being cooled and etched only once. This alternative method ove1.comes some difficulties, but introduces others. In particular, the incubation periods of the observed grains are unknown: any effect of crystal orientation on growth rate cannot be determined easily. A preferable method would be to measure the motion of a recrystallizing grain boundary with the sample at temperature without etching," but such measurements have in the past been restricted to nonmetals. This paper describes the construction and operation of a device, the goniometer furnace, with which the position of a moving grain boundary between a recrystallizing grain and the strained single crystal into which it grows can be measured by means of X-rays, with the sample maintained continuously at temperature. Goniometer Furnace The operating principle of the goniometer furnace is shown in Fig. 1. The sample, in the form of a bicrystal strip, is surrounded by a furnace, not shown in the sketch, and can be rotated about the two axes A and B which intersect at the point where the X-ray beam strikes the strip. The strip is oriented so that one of the two grains gives a strong Bragg reflection, which is detected by a suitably placed Geiger-Miiller counter coupled to a counting-rate meter When the strip is moved parallel to its own length in the furnace, arrow C, so that the X-ray beam strikes the second grain, there is in general no strong reflection. By noting the position of the strip at which the drop in Geiger counter reading occurs, it is possible to determine the position of the boundary. Measuring the change in boundary position with time at temperature gives the rate of growth of the recrystallizing grain. Details of the construction and operation of the goniometer furnace are given in the Appendix. Measurements showed that the temperature in the furnace was uniform within ±10°C over its working length of about 28 cm. The temperature at the measuring position, i.e., at the point where the X-ray beam struck the sample, was estimated to be constant within ±2oC. Using the goniometer furnace, the position of a stationary boundary could be measured with a reproducibility of ±0.3 mm. At elevated temperatures, 500" to 625"C, with the boundary in motion and the X-ray reflection less sharp, the estimated accuracy of each measured boundary position dropped to about ±1 mm. Experimental Results The test pieces were single crystals of 99.6 pet A1 —principal impurities 0.19 pet Fe and 0.12 pet Si— 1 mm by 1 cm in cross section and 6 to 10 cm in length, grown by the strain-anneal method. This relatively low purity material was used because of the difficulty encountered in producing strain-anneal single crystals of very high purity—99.996 pet—

Jan 1, 1957

By Richard J. Fruehan

ThE thermodynamic activities of nickel and chromium in liquid Ni-Cr alloys have not been previously reported. There have been several investigations on the solid alloys.1-3 In the present investigation the activity of chromium in liquid Ni-Cr alloys at 1600° C was determined by the use of the following galvanic cell, The use of galvanic cells employing solid oxide electrolytes for determining the activity of metals in solid alloys was first demonstrated by Rapp and Maak4 on Cu-Ni alloys between 700° and 1000°C. Recently Schwerdtfeger5 tested the performance of the ZrO2(CaO) electrolyte at 1600°C and found it satisfactory for oxygen pressures as low as 10"12 atm. He also demonstrated the use of solid oxide electrolytes for determining the activities in liquid metal systems in measuring the activity of manganese in Fe-Mn alloys at 1500°C. Extensive investigations have been carried out in this laboratory, exploring the oxygen partial pressure lower limit at which ZrO2(CaO) electrolyte can be used satisfactorily in oxygen galvanic cells at 1600°C. In a paper to be published at a later date,9 it is demonstrated conclusively that ZrO2(CaO) exhibits insignificant electronic conductivity at oxygen pressures down to about 3 x 10"13 atm which is lower than the oxygen partial pressure in equilibrium with Cr-Cr2O3 at 1600°C. Therefore, the activity of chromium can be related to the measured reversible electromotive force of the cell in the present investigation since no electronic short circulating will occur. Fig. 1 is a schematic diagram of the cell used. The Cr-Cr2O3 electrode was made of equal weights of chromium and Cr2O3 powders which were mixed and packed into a recrystallized alumina crucible. A Pt-wire lead was embedded into the Cr-Cr2O3 compact to insure good contact. A ZrO2(CaO) crucible, supplied by the Zirconium Corp. of America, contained the Ni-Cr melt equilibrated with solid Cr2O3. The ZrO2(CaO) crucible was placed on the Cr-Cr2O3 electrode and additional Cr-Cr2O3 mixture was packed around it. Contact with the Ni-Cr alloy was made with a Cr2O3 tube, which is a weak electronic conductor. A platinum wire lead was attached to the Cr2O3 tube. The galvanic cell was lowered slowly into the hot zone of the furnace tube in order to avoid too large a thermal shock which could break the ZrO2 (CaO) crucible. The furnace was con- tinuously flushed with purified argon during the experiment. The temperature was measured with a Pt-Pt/10 pet Rh thermocouple and maintained at 1600° ± 5°C. The electromotive force was measured with a recording potentiometer. The furnace was turned off when measurements were being made in order to avoid induction effects and the reversibility of the cell was demonstrated in the usual manner. The electromotive force was measured several times over a period of approximately 1 hr. During that period the electromotive force remained constant within ± 3 pet and did not continuously drift in any one direction. After the experiment the alloys were analyzed for chromium in the usual manner. The measured electromotive forces of the cell at 1600°C, (2912°F), are listed in Table I. The activity of chromium, with solid pure chromium as the reference state, (a), was calculated using Eq. [l], , n F E I, n lna RT- U] where E is the measured electromotive force, F is the Faraday constant, and n is equal to 3, the number of equivalents per mole, (nF/RT = 18.59 volts'1 at 1600°C). The resulting activities are listed in Table I. The activity of chromium relative to pure liquid chromium was also calculated. The free energy of fusion of chromium at 1600° C was calculated using

Jan 1, 1969

By Ferid Kromer

Geography: The Tagtepe district of the Vilayet of Eskigehir is about 20 miles northeast of the city of Eskigehir (approximately midway between Ankara and Istanbul) in western Anatolia. The area is a mountainous one, the highest peak being Tagtepe Mountain (5200 ft) which is approximately in the center of the district. The mountains drop off to the deep valley of the Sakarya River on the north and to the plain of Eskigehir on the south. FERID KROMER, Junior Member AZME, is a Consulting Mining Engineer and General Manager, Bagtag Turk Maadin Ltd., Istanbul, Turkey. New York Meeting, February 1950. TP 2629 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Dec. 29, 1948. For the most part, the watershed is on the northern side of the mountain barrier, draining into the Sakarya River, which in turn empties into the Black Sea midway between Zonguldak and the mouth of the Bosphorus. The approximate area covered by the Tagtepe district is shown in fig. 1. Transportation to shipping points is available via the Istanbul-Ankara railroad. The station on this line nearest the mining district is Alpikoy station, about 20 miles by road southwest of Tagtepe Mountain. Interior roads within the district are poor. Being of dirt, the winter rains and snows render them almost impassable for trucks from about the middle of December until the end of March, thus presenting a considerable transportation problem. However, the roads from the Bagoren and Tagtepe chromite mines to the railroad shipping point at Alpikoy station have recently been repaired and will be maintained for all-weather truck transportation. Detailed climatic data are not available. However, in general the spring, summer, and early autumn months are dry, and good weather may be expected from May until early November. Then the winter rains commence, and heavy snow is usual during January and February. Geology: The mountainous structure of Tagtepe belongs to basic rocks of serpentine (Variscan Orogeny) which is in contact with Paleozoic schists at west, and an Oligocene outcrop of red clays in Margi-Sepetci region (see fig. 1) at southeast. The northwest and southwest borders of Tagtepe district are, respectively, surrounded by Paleozoic schists and pebbly gray and yellow Neogene clays. More recent formations of alluviums overlay the plain of Eskigehir. Dark basic rocks of trachytes with hornblende are visible on Turkmenbaba Mountain, at the west of Tagtepe. Mineral Occurrences: Chromite: the most important mineral found in any quantity in the Tagtepe district. The alignment of the deposits of chromite is in general along the line Bagoren-Tagtepe (see fig. 1). The first mines in the area were those of Tagtepe and Bagoren, which were developed over 20 years ago with Swedish capital. Other deposits of chromite, more recently discovered and so far of less importance, are being worked at Kurucor, Komurcu, Gelinmezari, and Lacin (see fig. 1). Deposits average generally between 46 and 48 pct chromic oxide, with the exception of the Bagoren mine which averages 44 pct. However, a new lode, very recently plotted, in the Tagtepe mine averages 50 pct Cr,O,, 4.6 pct SOz, and 7 pct FeO. Geological character of the chromite occurrences in the Tagtepe mine may be considered typical of most chromite lodes in this area. The indications are that the formations of ore lenses are developed by the segregation of chromite crystals intruded into the serpentinized rock, and exposed later to tectonic movement within the zone of crystallization. All lenticular masses are more or less regular in shape and follow each other in southeast-northwest direction and dip generally 70" NE. Ore lenses do not seem to persist in depth, average depth of two lenses is 60 ft below surface. Three lodes .have been mined as open-pit. The average dimensions of individual lenses are as follows: pitch length, 100 ft; breadth, 27 ft; and width, 20 ft. The lenses and their enclosing rocks are broken by parallel fractures in approximately east-west direction. These joints are filled, except in one lode, with cementing material, which gives to the ore a

Jan 1, 1951

By Ferid Kromer

Geography: The Tagtepe district of the Vilayet of Eskigehir is about 20 miles northeast of the city of Eskigehir (approximately midway between Ankara and Istanbul) in western Anatolia. The area is a mountainous one, the highest peak being Tagtepe Mountain (5200 ft) which is approximately in the center of the district. The mountains drop off to the deep valley of the Sakarya River on the north and to the plain of Eskigehir on the south. FERID KROMER, Junior Member AZME, is a Consulting Mining Engineer and General Manager, Bagtag Turk Maadin Ltd., Istanbul, Turkey. New York Meeting, February 1950. TP 2629 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Dec. 29, 1948. For the most part, the watershed is on the northern side of the mountain barrier, draining into the Sakarya River, which in turn empties into the Black Sea midway between Zonguldak and the mouth of the Bosphorus. The approximate area covered by the Tagtepe district is shown in fig. 1. Transportation to shipping points is available via the Istanbul-Ankara railroad. The station on this line nearest the mining district is Alpikoy station, about 20 miles by road southwest of Tagtepe Mountain. Interior roads within the district are poor. Being of dirt, the winter rains and snows render them almost impassable for trucks from about the middle of December until the end of March, thus presenting a considerable transportation problem. However, the roads from the Bagoren and Tagtepe chromite mines to the railroad shipping point at Alpikoy station have recently been repaired and will be maintained for all-weather truck transportation. Detailed climatic data are not available. However, in general the spring, summer, and early autumn months are dry, and good weather may be expected from May until early November. Then the winter rains commence, and heavy snow is usual during January and February. Geology: The mountainous structure of Tagtepe belongs to basic rocks of serpentine (Variscan Orogeny) which is in contact with Paleozoic schists at west, and an Oligocene outcrop of red clays in Margi-Sepetci region (see fig. 1) at southeast. The northwest and southwest borders of Tagtepe district are, respectively, surrounded by Paleozoic schists and pebbly gray and yellow Neogene clays. More recent formations of alluviums overlay the plain of Eskigehir. Dark basic rocks of trachytes with hornblende are visible on Turkmenbaba Mountain, at the west of Tagtepe. Mineral Occurrences: Chromite: the most important mineral found in any quantity in the Tagtepe district. The alignment of the deposits of chromite is in general along the line Bagoren-Tagtepe (see fig. 1). The first mines in the area were those of Tagtepe and Bagoren, which were developed over 20 years ago with Swedish capital. Other deposits of chromite, more recently discovered and so far of less importance, are being worked at Kurucor, Komurcu, Gelinmezari, and Lacin (see fig. 1). Deposits average generally between 46 and 48 pct chromic oxide, with the exception of the Bagoren mine which averages 44 pct. However, a new lode, very recently plotted, in the Tagtepe mine averages 50 pct Cr,O,, 4.6 pct SOz, and 7 pct FeO. Geological character of the chromite occurrences in the Tagtepe mine may be considered typical of most chromite lodes in this area. The indications are that the formations of ore lenses are developed by the segregation of chromite crystals intruded into the serpentinized rock, and exposed later to tectonic movement within the zone of crystallization. All lenticular masses are more or less regular in shape and follow each other in southeast-northwest direction and dip generally 70" NE. Ore lenses do not seem to persist in depth, average depth of two lenses is 60 ft below surface. Three lodes .have been mined as open-pit. The average dimensions of individual lenses are as follows: pitch length, 100 ft; breadth, 27 ft; and width, 20 ft. The lenses and their enclosing rocks are broken by parallel fractures in approximately east-west direction. These joints are filled, except in one lode, with cementing material, which gives to the ore a

Jan 1, 1951

By C. S. Smith, K. K. Ikeuye

In an earlier paper1 one of the authors called attention to the significance of the relative free energies of grain boundaries and interphase boundaries in alloys in determining the shape and distribution of micro-constituents. The ratio of the interphase and inter-crystalline boundary energies (that is, —?12, where ?12 is the energy of the interface between a crystal of phase 1 and a crystal of phase 2, and ?11 is the energy of the boundary between two crystals of phase 1) will be denoted by F. It is this ratio that determines, by the simple triangle of forces relation, the dihedral angle, ?, of phase 2 where it adjoins a boundary between two grains of phase 1. On a metallographic sample various angles are actually obtained because of the random orientation of the plane of observation, but the statistically most frequent angle is the true one. These basic principles were discussed in detail in the earlier paper. The experiments described below show the effect of both composition and temperature on ? and T for some alloys containing a liquid phase, and provide data on the rate of approach to the equilibrium angles in both solid and liquid phases. All the alloys were melted in a graphite crucible and cast into ingots 3/4 by 11/8 in. cross-section. Some of the aluminum alloys consisted of two immiscible liquids from which uniform castings could not be obtained. The amount of liquid phase varied locally to a considerable extent and the analyses were meaningless. Nevertheless, the composition of the liquid would not differ from that in an alloy of the intended gross composition, and the synthetic composition of the alloys was therefore used in considering the surface energy results. The ingots were given initial deformation by cold-rolling to 50 pct reduction, annealed, and given a second 50 pct reduction prior to cutting into small samples for heat treatment at the times and temperatures subsequently reported. The resulting micro-samples were carefully prepared metallographically and examined at magnifications of 650, 1280, or 2500. The objectives used were 21X, 0.40 NA (dry); 41X, 0.65 NA (dry); and 80X, 1.40 NA (oil emulsion). The appropriate angles were measured by rotation of the stage of a Bausch and Lomb metallograph to align the appropriate boundaries successively with a cross-hair in a micrometer eyepiece. About 250 angles were measured on each phase. Though the angles were read to 1°, the accuracy is probably not above 3°, because of uncertainty in setting the cross-hair tangent to the sometimes curved boundary. The corners of very small particles, particularly in early stages of adjustment after cold-rolling, were difficult to measure and the results were slightly dependent on the magnification used (compare Fig 1-C and 1-D). With particles of larger size and more nearly equilibrium shape, magnification made no difference (vide Fig 1-F and 1-G). The measured angles were grouped in 10° intervals (5° if ? was less than 20°) and plotted in bar

Jan 1, 1950

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

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

Jan 1, 1961

By C. C. Templeton, J. C. Rodgers

A key step in feed water treatment for generating wet steam for thermal oil recovery is the removal of calcium and magnesiunt hardness by cation-exchange series softening. Knowing the solubility of any scale forming salts in brines at elevated temperatures is necessary for fixing the level to which the feed water must be softened. Such calcium sulfate solubility data, previously not available above 392F, were determined by the authors in a flow equilibrium apparatus mud will be reported elsewhere. These data were used to develop a method for predicting the solubility of anhydrite in hot water or steam droplets for saturated steam pressures as high as 2,000 psig (637F). (The calcium sulfate solubility product is represented by a combination of two factors, one reflecting the effects of ionic strength and the other accounting for the effects of complex ion formation in either calcium-magnesium-rich or sulfate-rich brines.) The method is applied to a calcium-magnesium-rich brine If moderately high salinity from a pilot hot-water flood, I nd to several sulfate-rich, low-salinity feed waters and l lowdown (cooled steam droplets) samples from steam s ak operations. The predicted calcium hardness levels corresponding to the calcium sulfate solubilities agreed reasonably well with the results of laboratory solubility determinations run on the field samples. Further testing of the method is needed for brines of other composition classes. Existing field cation exchange softeners in the cases tested are performing adequately since all the samples were found to be undersaturated with respect to calcium sulfate at their operating temperatures. Introduction Prevention of scaling caused by precipitation of calcium sulfate (anhydrite) is of considerable concern in connection with thermal recovery processes using wet steam or hot water. To avoid anhydrite precipitation in a heated system, an engineer must keep the product of the calcium and sulfate concentrations in the water or steam droplets below the value of the solubility product of anhydrite for the temperature and brine composition in question. Usually it is most practical to keep the concentration product lower than the solubility product by keeping calcium low in the presence of high sulfate, or by keeping sulfate low in the presence of high calcium. This can be done by a choice of combinations of natural waters and water treatment processes (such as series cation exchange softening to remove calcium). Until recently, few anhydrite solubility data, particularly for solutions containing other salts, were available for temperatures above 392F (211 psig steam); Marshall, Slusher and Jones' studied the CaS0,-NaCI-H,O system up to 392F and surveyed the work of previous investigators. To model natural brines, one needs to study the solubility of anhydrite in aqueous solutions of sodium chloride, sodium sulfate, calcium chloride, magnesium chloride and their mixtures. Since steam pressures as high as 2,000 psig (637F) may be involved in thermal oil recovery projects, a solubility study was conducted between 482 and 617F.' Discussed in this paper is the application of these data to the prediction of anhydrite precipitation in some practical steam soak and hot-water injection projects. Any simple method for predicting the solubility of an inorganic compound over a wide range of temperatures and solution compositions must be based on some assumptions, and therefore must yield approximate results. On the one hand, natural brines contain too many ionic species for all to be included in a simple scheme; on the other hand, there is no adequate theoretical basis for the exact prediction of solubility in even simple solutions of mixed electrolytes. However, it is possible at a given temperature to base a reasonable prediction scheme on two phenomena:'-' the increase in solubility with increasing total concentrations of all ions (as measured by the ionic strength; see the Appendix), and an increase due to formation of cornplexes between calcium ions and sulfate ions and between sulfate and magnesium ions. Stiff and Davis' developed such a scheme for predicting the solubility of gypsum (CaSO, ¦ 2H,O) in brines at temperatures u~ to 212F. However, for the higher temperaturei of present interest, the stable solid phase is anhydrite (CaSO,). This study involves a two-part method for predicting anhydrite solubility products. First, one predicts a value K, for a given ionic strength I and a given temperature T corresponding to mo./msr, = 1 from data of the CaS0,-NaCI-H,O system. Second, one determines a group of factors F .= F(Ca) • F(Mg) • F(SO,), where the individual factors account for increases in the solubility product due to complex formation by high concentrations, respectively, of calcium, magnesium and sulfate. Combining the two parts, one obtains the solubility product in molalities as

Jan 1, 1969

By D. C. Jillson

THE data on the critical resolved shear stress for zinc single crystals published by Rosbaud and Schmid1 showed many irregularities, as seen in fig. 1. There have been subsequent investigations,2,3 but no one has repeated this work with a wide range of orientations, with specimens of a higher degree of purity and perfection, and with improved experimental techniques in order to determine whether these variations were entirely experimental or whether they might have been due, at least in part, to some feature of the mode of deformation not known or understood. Mathewson4 and others have long felt that the glide observed in a [100]* direction between two (001)* planes in the zinc lattice might be actually the net effect of many consecutive unit glides or movements in two alternating [210] directions (fig.

Jan 1, 1951

By C. J. Hicks

The labor policy of the Standard Oil Co. (New Jersey) is founded first of all on paying at least the prevailing scale of wages for similar work in the community; on the eight-hour day at the refinery, with time and one-half for overtime; one day's rest in seven; sanitary and up-to-date working conditions; just treatment assured each employee; opportunity for training and advancement; payment of accident benefits beyond the amount prescribed by the State compensation law; health supervision by a competent medical staff; payment of sickness benefits after one year's service; coöperation with employees in promoting thrift and better social and housing. conditions; and assurance of a generous annuity at the age of 65, guaranteed for life after 20 years of service. Most of these features have been a part of the company's policy for many years, but it is only during the past two years that the cooperation of employees in determining these matters has been definitely assured through industrial representation. Industrial representation, in the Standard Oil Co. (N. J.), is a principle rather than a procedure. It is built upon the belief that personal association of those interested in any problem leads to a mutual understanding and a fair decision as to what is right. Fully believing in this principle, representatives of employees and representatives of management evolved a simple plan, the basis of which is that it gives every individual employee representation at joint conferences on problems and fundamental principles affecting all those interested in the industry. It is based on cooperation, not antagonism; its operation makes perfectly clear both to management and to employees that their interests are identical, and not at variance with the interests of the stockholders, and that mutual understanding and cooperation insure progress and success for all. Furthermore, experience has definitely shown that representatives of the employees are not only alert for the employees' interests but are as keen as the representatives of the management in determining and insisting upon fairness to the employer. Though the plan has been in operation nearly two years, it is an experiment, in that, being based on a principle rather than on cut-and-

Jan 1, 1921

By W. B. Phillips

The earliest mention of the sulphur deposits in what is now Culberson County, Texas, seems to be contained in " Explorations and Surveys for a Railroad Route from the Mississippi River to the Pacific Ocean, United States War Department, 1853-54." Captain John Pope (he was not commissioned Captain until 1856) had charge of one of the divisions of the Survey. In his report on the geology of the route, William P. Blake noted the analysis of a greenish earthy powder from the bed of Delaware Creek, at the springs, which contained 18.28 per cent. of free sulphur. The report states: "From the chemical examination of the waters of the spring, by Dr. Booth, it appears that chloride of sodium is the principal solid ingredient, but considerable quantities of sulphide of sodium are present. ***** The waters from the springs examined by Dr. Booth were alkaline, but it is possible that some of the springs are acid; and in this case the precipitation of sulphur would ensue on the mixture of the acid waters with those charged with alkaline sulphurets and the origin of the deposits of sulphur would be thus explained." This is the first reference to the existence of sulphur in that region, the first mention of the character of the water found there and the first suggestion as to the origin of the deposits. The possibility of the existence of acid waters was confirmed by E. M. Skeats, nearly 50 years later.' In this publication, Skeats says that the water from the sulphur deposits in Section 11, Block 114, Township 6, contains 79.08 grains of free sillphuric acid per gallon. This locality is about 13 miles (21 km.) south . of Delaware Creek and about 35 miles (56 km.) east of the Delaware Springs. The next published reference to the existence of sulphur in Trans-Pecos. Texas is in the Pirst Annual Report of the Geological Survey of Texas, 1889, page 226, where W. H. von Streeruwitz mentions that sulphur is found in that region, but gives no further information. In the

Jan 1, 1918

By C. S. Blair

THE development of a geological department as an integral part of the Tennessee Coal, Iron & Railroad Co. in the Birmingham district, Ala-bama, in 1908 was an innovation probably unique for any mining organ-ization south of the Ohio River, At that time a few of the oil companies were starting geological departments, but there were no geologists among the larger industrial organizations. The Tennessee Coal, Iron & Railroad Co. had been a substantial producer of pig iron for many years and was just getting a start in the manufacture of steel products from the pig iron. It had large acreages of coal land, ore land and timber land, but there was lacking the detailed knowledge of the possible mineral resources of much (of its territory, and this territory at that time covered an area in the neighborhood of 500,000 acres in the states of Alabama, Tennessee and Georgia. Those responsible for the operations of the mining properties, not being familiar with the kind of help that might be expected from geologic work, were decidedly skeptical of the utility of the work. Therefore it was necessary to develop cooperation with the mining organization, by not infringing upon its functions, and by developing the work in such a manner as to demonstrate to the mining department its practical utility. In the first instance the man responsible for a mining operation is apt to assume the attitude that the geologist is a blockader, because the geologist, unfortunately, is obliged to point out difficulties in the carrying out of mining operations in the way originally planned. He points out the dangers of mining out one coal or metal seam at the ultimate expense of an upper or lower seam, and he develops structural features, such as faults and folds, which call to the attention of the mining operator diffi-culties in his future operations, which the latter had not anticipated. Eventually, however, -the value of having these data became ap to the Tennessee Coal, Iron and Railroad Co., and the operators not only welcomed the geological work and cooperated fully in its acquisition of essential information, but reached the point of asking assistance and advice; and complete coordination of the two activities has existed for many years.

Jan 1, 1933

By Reginald Williams

THE amount or value of the precious metals consumed in dentistry is probably amazing to most people. It falls very little short of that which is consumed in jewelry. Inasmuch as the ultimate destination is in the human mouth, dental alloys enjoy some importance because life and health depend upon restorations made with them. Prosthetic dentistry has made wonderful progress in the last few years. The manufacturers who supply the metals also deserve commendation. This industry which deals with metals to go into people's mouths is comparatively new. There is no literature on the subject, and little or no precedent by which to be guided. It was only by close cooperation with the dentist or prosthetic technician that desirable physical properties were produced, as nearly as possible, in the metals which were available and permissible. It is true that there were and still are conflicting opinions among the dentists as to the physical properties they require. Sometimes they request the impossible, such as alloys which are exceedingly stiff and springy, yet will bend or adjust easily. Even in this latter instance, progress has been made by supplying methods of heat-treatment whereby metals may be softened or hardened at will. (Figs. 1 and 2.) The demands made upon manufacturers are extremely varied. They must supply metals of tensile strengths ranging from approximately 30,000 to 100,000 lb. per sq. in. and over. The latter metals must be workable and in many instances capable of extreme deformation. They must not be affected by mouth conditions, nor should they oxidize greatly when molten, at red heat, or during a soldering operation. In addition to physical specifications, color demands must also be met. The firm of which I have the most knowledge manufacturers 11,553 standard stock articles of precious metals, taking into consideration formulas, finenesses, grades, colors, gages, lengths, sizes and weights. If special demands are taken into consideration, the number would be in excess of 25,000. Wrought metals are manufactured in a great many alloys of different sizes and shapes, such as plate, bar, rod, wire, sheet, strip, mesh and foil. There are also other products of importance.

Jan 1, 1928

By O. D. Gonzalez, R. A. Oriani

A thermo-osmosis technique has been used to measure the heat of transport, Q* , of hydrogen and of deuterium dissolved in a iron and in nickel, and of hydrogen in Feo.6Nio.4 in the tempevature range 400° to 600°C. For all these systems, Q* is negative and has a large temperature coefficient; an isotope effect can be established for the solutes only in nickel. The magnitude of Q* is considerably larger than the activation energy, E , for migration in the case of these isotopes in a iron, so that all variants of the Wirtz model must be rejected. The phenomenological definition of Q* is developed to show that Q* is related to the mechanisms by which the activation energy is dissipated back into the lattice, and that Q*/E is a function of the ratios of the mean free paths of electrons and of phonons to the distance of jump of the diffusing atom. A correlation is shown to exist between the sign of Q* in thermal diffusion and that of the effective charge in electro migration, and may be understood as due to the large ratio of the mean free path of electrons to that of phonons. THE study of nonisothermal diffusion in the solid state is of interest because certain aspects of the mechanism of diffusion are made manifest which remain concealed though still present in the isothermal case. The thermodynamics of irreversible processes characterizes nonisothermal diffusion, known as thermal diffusion or as the Ludwig-Soret effect, by a quantity, Q*, called the heat of transport, which essentially measures the sign and the magnitude of the steady-state concentration gradient produced by the imposed temperature gradient. The problem then is to understand the quantity Q* at the atomistic level. There does not exist a theory for the atomistic interpretation of the heat of transport. There are, however, two classes of simple models which seem to afford some physical insight into Q*. Wirtz's model1, z and its subsequent generalizations partition the activation energy, E, for the migration of the atom spatially about the region of the migrating atom, so that Q* is the difference between the portion of the activation energy centered about the original site of the jumping atom and that portion about the arrival site. Clearly, the magnitude of Q* cannot on this model be larger than the activation energy for migration. The model of Oriani3 also considers the spatial distribution of E not only before but also after the atomic jump, and Q* is related to the variation of the spatial distribution of E that is produced by the jump. The simplest kind of system with which to compare the consequences of these ideas is the interstitial solid solution, since one may easily choose a temperature at which only the interstitial component moves, the solvent lattice serving as a completely satisfactory frame of reference. Thus, one avoids complications arising when both species in a binary system move. In addition, one avoids the necessity of knowing the energy for the formation of a vacancy, something which is needed for the analysis of thermal-diffusion data on metals which diffuse by the vacancy-exchange mechanism. However, the number of well-measured interstitial systems is extremely small, and, in particular, there are almost no data in the published literature for the temperature dependence of the heat of transport. If one works with solutes which are gases in the pure state at ordinary temperatures, one may use the technique of thermo-osmosis4 which permits thermal diffusion to be measured over a small temperature difference so that the temperature dependence of Q* can be more easily determined. The choice of dissolved hydrogen in iron and nickel was based on these considerations as well as on the desire to look for an isotope effect associated with localized

Jan 1, 1965

E. T. DUMBLE, Houston, Tex.-This paper is a continuation of one that was published by Mr. Garfias, I believe, in the Journal of Geology, 1912, in which he gave the results of his investigations in Mexico, showing that the basalt extrusions frequently did not come up as cones. but reached the surface as a small neck and then mushroomed out into a sill, penetrating the beds both in limestones and in shales. He has continued his investigations to show that as these basalt protrusions came up they forced the strata into a funnel shape at the top instead of throwing them out altogether. While this may be true concerning these particular beds, there are other places at which the basalt does appear clearly as cones and dories, and there the funnel structure does not exist. We know that the sills are there, because we find them in the wells. In one well that I know of. we found a 2-ft. sill of basalt at about 1600 ft. and oil below it at about 2100 ft.; others have gone through similar beds. We also know that there. are cones, because north of the Ranuco River one well struck basalt at about 800 ft. and continued in it for several hundred feet-did not pass through it at all. This paper of Mr. Garfias will give us considerable help in that oil field. W. E. WRATHER, Wichita Falls, Tex.-I would like to ask for information as to the temperatures of Mexican oils. I have heard a number of conflicting reports about the high temperatures of the water and oil, and the relationship between them.

Jan 1, 1918

By Francois E. Heuze

The Crestmore Mine of the American Cement Company lies at the eastern end of the Jurupa Mountains, 50 miles east of Los Angeles. Originally, a quarry was opened in 1908 for "limestone" used in the manufacture of cement. The mining operations eventually went underground employing first a modified system of block caving and later the "room and pillar" scheme. The limestones are relatively small roof pendants preserved in an enveloping and intrusive quartz diorite. They occur as two irregular lenticular bodies roughly parallel at the top and tending towards convergence at depth. Their dip varies between 25 and 30 degrees E. The presently mined lower bed, Chino limestone, is typically composed of alternating bands a few inches to a few feet thick of medium to coarsely granular white crystalline limestone and somewhat yellowish limestone (brucite marble). A "room and pillar" scheme of mining is currently employed in the lower body of the Crestmore Mine. The levels are horizontal and access is provided by a spiraling road starting in the old quarry. The present depth of operations is an average 750 ft below the surface. Fig. 1 gives a three-dimensional general sketch of the mine. The long axis of the rooms is in an E-W direction, normal to the strike of the beds. Fig. 2 is a horizontal map of the 130 level, the deepest level mined presently. It is in this level that most of the in-situ investigations have been conducted. The present investigation was made possible by a non-restrictive grant of the American Cement Company to the University of California. The program included a series of in-situ tests using flat-jacks, plate bearing,

Jan 1, 1968

By O?Harra B. M.

THE work here described had for its purpose the procuring of data from which some quantitative estimate might be made of the results obtainable by using oxygen-enriched air in roasting zinc ores on a commercial scale. The principal metallurgical advantages of using enriched air in roasting zinc ores would be: 1. The rate of roasting would be increased, with consequent gain in the capacity of the roasting furnace. 2. As less air would be required for roasting, the volume of hot gases leaving the furnace and the heat carried out of the furnace as sensible heat in these gases would be less per ton of ore roasted; partly for this reason and partly because of the increased quantity of heat generated in the furnace by the larger amount of ore that could be roasted, the consumption of fuel by the furnace would be lessened; and by the use of air sufficiently enriched with oxygen the necessity of using fuel might be entirely obviated. 3. Roaster gas having a higher SO2 content could be produced; this would make possible greater capacity and more economical operation of the sulfuric-acid plant. Certain phases of the application of enriched air to roasting can be worked out only by experimenting with a furnace of commercial, or at least semicommercial, size. Thus the precautions necessary to secure proper. distribution of heat in the furnace;1 the volume of enriched air; and the proportion of oxygen in this air, necessary to give the desired increase in roasting capacity of the furnace and in SO2 content of the roaster gases;; and the most desirable frequency of raking, thickness of

Jan 11, 1924

By George Bain

SOME problems concomitant with commercial exploitation of marble are presented as examples of interesting, useful and profitable fields for application of scientific knowledge. The marble industry is only one such field and is selected because its varying new aspects are familiar to the author. However, what is true for marble is equally so in principle for many industrial minerals. The problems of any stone industry are to maintain markets, create new outlets for stone already in demand, and develop varied uses for varieties that are not so popular. Here the geologist has a different role from most of his colleagues in metal mining. The producing branch may ask about the expectable variation in thickness or size of a deposit as development proceeds. The stock department may call for the available amount of a given type of stone before accepting a large order. The sales force requires data on the use for stone from certain parts of deposits in order to divert grades to the most suitable use. The service depart-ment wants defects rectified and the cause determined to avoid recurrence. The mills want data on durability and cutting quality of abrasives. The geologist occupies no special department; he is on general call, as may be illustrated by a few types of problems that may be classified as: (1) dominantly geological in character, (2) dominantly chemical in character, (3) dominantly physical in character.

Jan 1, 1940

By P. S. Kotval

THE nominal composition of "hconel" alloy 718 is 53 pct Ni-19 pct Cr-19 pct Fe-3 pct Mo-5 pct Cb-0.8 pct Ti-0.6 pct A1-0.05 pct C. The nature of the fine strengthening phase in this alloy has been open to debate. iseelstein' has identified the strengthening phase in the matrix of "Inconel" alloy 718 as a colum-bium-rich fcc y' precipitate. Wagner and Hall2 have noted that the metastable y' precipitate overages to an orthorhombic Ni3Cb precipitate which manifests itself as an acicular phase. These authors thus clarify Kaufman and Palty's earlier suggestion3 that the strengthening phase is orthorhombic NisCb. Wagner and Hall's review also reports work by cometto4 which suggests that the fine strengthening phase is not fcc / but bct with a Ni3V type structure and based on the Ni3Cb composition. Kir man and warringtons have shown by analysis of electron diffraction patterns that the metastable strengthening phase in a 55 pct Ni-15 pct 0-25 pct Fe-5 pct Cb alloy is bct and based on the Ni3Cb composition. Raymond~ has provided electron diffraction evidence which indicates that "y'" in "Inconel" alloy 718 is bct in structure. This note presents unambiguous data on the structure of the strengthening phase in "Inconel" alloy 718* ihe samples of this alloy were provided by courtesy of the ASTM task group on phase identification in 'superalloys. after prolonged aging. The electron diffraction patterns presented show that strengthening phase is not y' but bct as was proposed by cometto,' supported by Raymond,~ and identified by Kirman and warringtons in a similar system. Fig. 1 shows a selected-area diffraction pattern taken from a thin foil of "Inconel" alloy 718. The sample had received a final aging treatment of 1118 hr at 1200°F to precipitate the strengthening phase in the matrix. Fig. 2 is a schematic representation of the features in the diffraction pattern. The matrix orientation is (0i2)~,, as is shown by the indexed zone in Fig. 3. Figs. 4, 5, and 6 illustrate that the pattern, Fig. 1, is composed of three bct zones, viz., (0i4), (2i0), and (i01), respectively. These three zones correspond, respectively, to the alignment of the c axis of the bct unit cell with the [001], [loo], and [OlO] directions of the fcc matrix and serve to illustrate the fully coherent relationship of the precipitate structure with the matrix. The streaking of certain reflections is also consistent with the above orientation relationship. The interpretation of the diffraction effects presented here shows the metastable strengthening precipitate in "Inconel" 718 alloy to be bct in structure and demonstrates that it is not an ordered fcc y' phase.

Jan 1, 1969