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By T. P. Chen, F. W. Bowdish

Studies made with a captive bubble apparatus on the sulfidization and collection by amyl xanthate of true chrysocolla specimens have defined the ranges of pH value and sulfide concentration which permit contact between the bubble and the mineral surface. Titanium compounds were the most effective of the materials found to activate the sulfidization of chrysocolla. With titanium activation, the contact angles and the ranges of pH value and sulfide wncentration giving bubble contact were all increased. Chrysocolla ores were concentrated by flotation. Chrysocolla ores occur at many localities in grade and quantity sufficient to make mining and millin feasible, but no satisfactory method of concentratio has been found. Although chrysocolla may be leached with acid, only those ores without acid-consuming gangue may be leached economically. Because of its potential importance, a study of the conditions nece sary for flotation of chrysocolla has been carried ou The literature contains a few references to flotation of chrysocolla. Two methods were developed by the U. S. Bureau of Mines.1,2 The first consisted of a fatty acid soap and a high xanthate as collectors of chrysocolla from a synthetic ore, while the second involved the use of hydrogen sulfide and xanthate. Ludt and DeWitt3 demonstrated the difference in adsorptive powers of chrysocolla and quartz for bas triphenyl methane dyes and suggested the use of butyl, hexyl or octyl-substituted malachite green as collector. Jackel4 emphasized the effects of combin tions of reagents such as Aerofloat 31, pine oil, and Reagents 404 and 425 with sodium sulfide and zinc hydrosulfite as conditioning agents. Although he reported recoveries of 89% from a synthetic ore and 98% from a natural ore containing azurite, malachite, chalcopyrite and chrysocolla, careful application of Jackel's method to chrysocolla from Tyrone, N.M., failed to give a high recovery. MATERIALS AND TECHNIQUE Samples from Inspiration, Ariz., and Tyrone and Magdalena, N. M., were used for experimentation and verified as true chrysocolla by leaching tests, specific gravity tests and X-ray diffraction. Chrysocolla does not dissolve at pH 4, although malachite and azurite do. Chrysocolla is about half as dense as the copper carbonates. X-ray diffraction analyses by the powder camera method confirmed the samples as true chrysocolla. A captive bubble apparatus, which cast an enlarged image of the air bubble and the mineral surface upon a screen, was used to check on the character of the surfaces. The specimens were prepared by grinding a flat surface on a glass plate using fine abrasive; then they were washed and kept in distilled water until they were to be treated with reagents. Before each reagent treatment, the specimen was carefully checked for cleanliness in the captive bubble apparatus. It was assumed that the surface was clean if, after fine grinding and washing of the specimen, the bubble would not stick. Specimens were handled with glass forceps, and precautions were taken to avoid contamination of the mineral surfaces. Contact angle measurements were carefully made several times on each treated specimen to obtain reliable average values. EFFECT OF pH VALUE AND SODIUM SULFIDE CONCENTRATION In each experiment, a specimen with a freshly ground surface was immersed for 10 min in a solution of sodium sulfide, washed and immersed for 15 min in a solution containing 30 mg per 1 of potassium amyl xanthate. The specimen was then washed again in distilled water and tested for contact angle in the captive bubble apparatus while submerged in distilled water. In this series of experiments, the pH of the sulfidizing solution was varied from 3 to 7, and the concentration of sodium sulfide, containing 60% Na2S, was varied from 50 to 650 mg per 1. Many combinations of pH value and sulfide concentration resulted in no contact between the bubble and the surface, but over a limited range of conditions, contact angles varying from 24ºto 52ºwere obtained. The data in Fig. 1 show sulfidization conditions that lead to bubble contact and those that do not. The region of contact is surprisingly small, which may indicate why flotation of chrysocolla involving sulfidization has proven so difficult in practice. Several features of the system are illustrated in Fig. 1. In the region between pH values of 4 and 6 with sodium sulfide concentrations below about 350

Jan 1, 1963

By Y. C. Liu, W. R. Hibbard

Based on pole figure data and microstructural observations, the re-crystallization orientation found in a copper strip previously cold-rolled 99.5 pct from a single crystal with an initial (110) [112] orientation may be described as: a 30° rotation, clockwise and counterclockwise, about octahedral poles of the cold-rolled texture such that all four poles function at a low annealing temperature (400°C) and only three of them function at high temperatures (500' to 1050°C). The relative intensity of deformation stresses on various slip planes can be correlated with the choice of poles affecting the rotations found in the recrystallized orientations. ROTATIONAL reorientation about the poles of densely packed crystallographic planes is an important characteristic of secondary recrystallization" in face-centered cubic metals. Some evidence has also been interpreted to show that such a rotational relationship also exists in the primary recrys-tallization process." In an investigation of the crystallographic relationships in the recrystallization process, several aspects of the experimental procedure should be considered. With cold-rolled poly-crystalline metal as the initial material, pole figure analysis leaves many ambiguities as to whether or not simple indices can be assigned to adequately represent its orientation. The rolling texture does not consist of a single texture. Minor deformation textures are usually present. In all cases, twin textures are present. The presence of both minor and twin deformation textures influences the recrystallization texture. In order to study the recrystallization mechanism, a more precise knowledge of the history of the material before recrystallization is necessary. Tensile deformation of a single crystal usually produces residual stresses which are concentrated at slip bands. Since the exact nature and orientation of these potential nuclei sites cannot be experimentally evaluated, the tensile deformation of a single crystal was not considered adequate. From the work done by Barrett and Steadman6 n copper, it appeared that cold rolling of a single-crystal specimen with an initial (110) [112] orientation would yield a specimen which fulfills the conditions required for the present investigation, namely a highly preferred single rolling texture with relatively homogeneous stress distribution. By investigating the recrystallization texture of this material, additional details of reorientation during recrystallization might be obtained. The purpose of this paper is to describe such an investigation. Experimental Procedure Copper used in the present investigation was cathode sheet with a purity of 99.94 to 99.97 pct. A copper single-crystal specimen, 1.15x0.8720x0.5322 in. (thickness) was cut from a cylindrical crystal which was grown in a Bridgman furnace.' The cutting was accomplished on a horizontal milling machine operated at a very slow speed to obtain a (110) plane in the rolling plane and a [112] direction in the rolling direction. The disturbed surface was removed by electrolytic polishing in dilute orthophos-phoric acid (H3PO4) with a specific gravity of 1.14, and a current density of about 1 to 2 amp per sq cm. A 3-min polishing was needed to eliminate the disturbed surface causing Debye-Scherrer rings and a 45-min polish produced a surface which yielded sharp rounded Laue spots. It was estimated that about 1/16 in. of metal was removed from the original cut surface. The final orientation of this specimen before rolling was about 2" from the (110) plane in the rolling plane with a [112] direction aligned in the rolling direction. It is possible that a small amount of strain was still present in the cube despite the fact that the Laue spots seemed very sharp. It is doubtful, however, that this would be an important factor after a subsequent rolling reduction of 99.5 pct. This copper specimen was rolled on a laboratory rolling mill with two highly polished rolls 37/8 in. in diam in the following manner: 0.010 in. per pass to 50 pct reduction, 0.005 in. to 70 pct, 0.002 in. to 85 pct and, finally, 0.001 in. per pass to a 99.5 pct reduction. Specimens, about 1 in. sq with the rolling edges intact, were cut from the rolled strip by the electrolytic method previously described, after the strip

Jan 1, 1954

By A. R. Troiano, A. B. Greninger

There is need for an adequate working hypothesis that would describe at least qualitatively the crystallographic mechanism for the transformation from austenite to martensite in steel. A general theory would not only be of great assistance in the correlation of existing data and in planning future experimentation, but would also form the basis for an eventual explanation of the property changes that accompany lattice transformations. The mechanism of martensite formation described in the following pages is the outcome of two new experimental determinations: (1) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite, and (2) the measurement and analysis of the change in position that a volume of austenite undergoes when it transforms into a crystal of martensite. For this latter study, the stereographic analysis of shear was employed; this method greatly simplifies the solution of lattice-shear problems, and some space is devoted to its description. Lattiice Relationships and Habits PREVIOUS WORK The lattice relationships between austenite and martensite in carbon steels have been studied by Kurdjurnow-and Sachs,' and by Wassermann;2 and in iron-nickel alloys by Nishiyama.3 Wassermann,2 and Mehl and Derge.4 The studies by Kurdjumow and Sachs and by Wassermann were made on single (austenite) crystals of quenched 1.4 pct carbon steel, and the results of these two independent studies agree closely with the postulated lattice relationships: (III)r||(0ll)a [101]r [111]a [1] Both Nishiyama and Wassermann worked with an alloy of iron plus 30 pct nickel (all austenite at room temperature), and "martensitic alpha" was formed by cooling in liquid air. They agree that the lattice relationships for these conditions are: (lll)r||(011)a [112]r[011]a [2] Mehl and Derge worked with a range of iron-nickel alloy compositions centered about 30 pct nickel. They concluded that when the transformation takes place near room temperature or above, relationship [l] holds, but if the same specimen is made to transform at -195°C, relationship [2] obtains;intermediate temperatures evidently produced a combination of these two relationships. Sachs and co-worker~,1,7 as well as Nishiyama,3 have proposed transformation mechanisms for martensite formation.* Both of the mechanisms picture the transformation as initiated by shearing movements along the octahedral [Ill] plane of austenite, followed by suitable expansion and contraction to complete the transformation. These mechanisms have been described and commented upon by Mehl, Barrett, and Smith,8 Mehl and Derge,4 Wassermann,2 and others, and generally accepted by investigators in this field. Greninger and Troiano9 have recently published the results of a detailed study of the shapes and orientation habits of martensite crystals in plain-carbon and nickel steels. They found that, contrary to previous assumptions, martensite plates form not along the octahedral planes but along austenite planes of very high indices; these results were in line with those of previous studies of martensite reactions in nonferrous alloy systems by Greninger and coworkers.6,10 Greninger and Troiano concluded that the transformation theories of Kurdjumow and Sachsl and of Nishiyama3 are untenable. Phragmén11 reached a similar conclusion. EXPERlMENTAL METHODS The object of this particular study was the evaluation of (1) lattice relationship between austenite and martensite, and (2) relationship between the martensite lattice and the martensite plate. The technique used for solving these problems was similar to that used by Greninger6 on martensitic structures in 8 copper-aluminum alloys. Briefly, the method consists of grinding and polishing a specimen on a surface parallel to an individual martensite plate and thus exposing a single martensite crystal for an area of l to 3 mm. The orientation of this exposed martensite crystal is then determined by means of a back-reflection Laue X ray pattern.12 Another pattern is obtained from the matrix crystal, and a stereo-graphic plot of data from these two patterns then provides the solution to the problem. It is necessary to repeat this process on several crystals in order to determine whether or not the solution is unique.

Jan 1, 1950

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By Y. Kondo, S. Yamazaki, Z. Asaki

Thermal deco7nposition of Pyrite particles in a fluidized bed with inert gas stream was studied. Assuming that heat transfer from the surroundings to the fluidized particles controls the overall decomposition rate, rate equations for the batch process and for the continuous process were derived. In the batch experiment, a linear rate equation satisfies the experimental results and the overall heat transfer coefficient calculated from the rate constant agrees fairly well with that obtained by Leva.l1 For the continuous process, two rate equations were derived, one on the assumption of complete mixing of particles and another on the upward piston flow of particles in a fluidized bed. The former holds for a bed containing a higher fraction of decomposed pyrite realized at lower feeding rates. The latter can be applied for a bed at higher feeding rates. Thus, segregation of particles in the fluidized bed was indicated at higher feeding rates. Bed temperatures also correspond to these conditions. ThERMAL decomposition of pyrite may be represented by Eq. [I]. The pressure of diatomic sulfur gas reaches 1 atm at about 690°C. The thermodynamics,' kinetics,2'3 composition, and properties3-5 of decomposed products of such a reaction have been studied. Pyrite is a very common sul-fide mineral and is often accompanied with other sul-fides. It is of basic interest in nonferrous metallurgy to clarify the behavior of pyrite in the pyrometallur-gical processes of sulfide minerals of metals such as copper, lead, zinc, nickel, and so forth. Interest in this reaction increased recently because of possible elimination of arsenic from pyrite in processing highly purified iron oxide pellets. Producing elemental sulfur from pyrite, instead of sulfuric acid, also aroused interest in this reaction. It is indicated that the thermal decomposition of solid particles, such as calcium carbonate, proceeds through three major sequential steps: heat transfer, interfacial chemical reaction, and mass transfer.637 It is known that the decomposed product of pyrite is very porous2, 3 and the diatomic sulfur gas evolved can easily escape through this layer of decomposed product. It depends upon the circumstances, therefore, whether the heat transfer to the interface within particles or the chemical reaction at the interface determines the overall decomposition rate. The enthalpy change in the decomposition of pyrite is about 33 kcal per mole FeS2 which is comparable to that of calcium carbonate. The decomposition of calcium car- bonate becomes more and more dependent on the rate of transport of heat when reaction temperature increases, such as occurs in a fluidized bed.6'7 It is reasonable to presume, therefore, that the thermal decomposition of pyrite, an endothermic process, carried out in a fluidized bed may be analyzed according to the heat transfer controlling model. This work intends, first, to propose a mathematical model that determines the overall rate in a fluidized bed for the decomposition process and, second, to investigate a few characteristics of the fluidized bed based upon the experimental results obtained. KINETICS OF THERMAL DECOMPOSITION IN A FLUIDIZED BED It is intended in this section to obtain rate equations for thermal decomposition of pyrite in a fluidized bed by assuming that the overall rate is determined by heat transfer from the surroundings to the particles. Both batch and continuous processes are considered. 1) Batch Process. To obtain the rate equation in the batch process, the following two additional assumptions are made. First, the temperature of preheated inert gas, tg, blown into the fluidized bed is assumed to be the same as the temperature of the fluidized bed, tf. Thus, no heat exchange occurs between the gas and particles in the bed and only the heat transfer from the reactor wall kept at tw to the particles is to be considered. Second, the decomposition is assumed to start at the outer surface of the particles and to proceed toward the center. At any given time during decomposition, undecomposed pyrite remains in the tori at a temperature: td. The decomposed shell is composed of FeS1+x whose outer surface is at tp Diatomic sulfur gas evolving at the interface is heated to tf during its escape through the decomposed shell. This is illustrated in Fig. 1. With the above-mentioned assumptions of heat transfer, we have:

Jan 1, 1969

By G. Purcell, S. C. Sun

In an attempt to determine the relative collecting ability of 18-carbon fatty acids, studies were performed on rutile in aqueous solutions of the fatty acid soaps. The preceding article reported the electro-kinetic properties; this article outlines the flotation behavior. Results of these flotation experiments are described and correlated with the electrokinetic results. Recent studies of the electrokinetic1-4 and the electrochemical5,6 properties of a few solid-liquid interfaces have provided a better understanding of the flotation process. A number of investigators have attempted to determine the relative collecting ability of 18-carbon fatty acids, but their published results (even for the same mineral) vary widely. Such lack of agreement indicated a need for further investigation. In an effort, therefore, to resolve the problem, electro-kinetic studies were made on rutile in aqueous solutions of the fatty acid soaps. Following the determination of the electrokinetic properties, the flotation behavior of rutile was studied. Results of these flotation experiments are described in this paper and are correlated with the electrokinetic results. MATERIALS AND EXPERIMENTAL PROCEDURE Materials: Pure -28, + 35-mesh rutile crystals were used for all flotation tests, and nitrogen-saturated conductivity water was used throughout. Sodium hydroxide and hydrochloric acid were added for pH regulation. The methods of purification for these materials and the preparation of the soaps have been described elsewhere. 7 Equipment: A Hallimond cell, constructed in a manner similar to that described by Fuerstenau, Metzger and Seele,8 was used for the flotation of mineral particles; however, a coarse pyrex frit was substituted for the capillary. Procedure: Purified nitrogen was led through a two- way stopcock into a graduated cylinder partly filled with water. The gas forced water from the cylinder back into a header tank until the water level in the cylinder coincided with a predetermined mark. Reversal of the stopcock then allowed water in the tank to force nitrogen into the cell until the water in the graduated cylinder rose to a second predetermined mark. In this way a constant volume of nitrogen under practically constant pressure was used for each flotation test. However, the flotation time varied, depending upon the amount of mineral floated and the pH of the solution. Rutile crystals were transferred under water from a storage bottle by a glass scoop holding 1.7 g. Consistency of the scoop samples was good, varying from a low value of 1.67 to a high of 1.74 g. The water added to the conditioning bottle during mineral transfer was drained off, and then 2 cu cm of either hydrochloric acid or sodium hydroxide were added. The concentration of pH regulator was adjusted to give approximately the final soap solution pH that was required. The order of addition of reagents did not affect the results within the limits of experimental error. Soap solution of the required concentration was added under nitrogen pressure to fill the bottles completely. Conditioning for 1 hr was carried out on rolls rotating at 35 rpm. After conditioning, 2.5 cu cm of solution were run off into the container of a Beckman (model G) glass electrode pH meter. The electrodes were rinsed in this solution, which was then discarded, and 2.5 cu cm more were added for pH determination. The remaining solution and the mineral were transferred to the cell; care was taken to ensure that all mineral was washed out of the bottle by the conditioning solution. With the cell back in its flotation position the liquid just reached the desired level, and the test was started immediately. The amount of agitation in the cell was kept constant, and flotation was carried out without the use of a frother. In each series of ten tests one was run with no collector added to ensure that the mineral had not become contaminated, and two were conditioned at the same pH to check reproducibility. After each test the cell was dismounted, soaked in cleaning solution, washed in hot water and then rinsed with distilled water.

Jan 1, 1963

By M. Bevis, E. O. Fearon, P. C. Rowlands

Fe-Ni and Fe-Ni-C martensite specimens have been deformed in compression at room temperature and the habit planes of operative deformation twins determined by two-surface optical trace analysis. The full orientations of the martensite crystals were determined from divergent X-ray beam diffraction patterns. The experimental results are in excelled agreement with predicted twinning modes. In particular, the habit planes of some deformation twins in bcc martensites are consistent with a "Type XI compound'' twinning mode with Kl, Kz, 71, 77~ elements given by {5, 8, 11) {ioi}, (33) (ill) Tetragonal derivatives of this mode are operative in bct martensites. UnUSUAL deformation twinning modes have been reported by Richman' to occur in Fe-Ni-C martensites with bcc and bct structures. The twin habit planes were determined by single-surface trace analysis (pole locus method) and the remaining twinning elements were determined from the geometry of twin-twin intersections. The indices assigned to the observed habit planes are (3 101, "(089)" and "{0, 1,13)" or "{1,2,7} ", and only in the first case do the twinning elements correspond to a predicted twinning mode. This is mode 1.4 in the paper by Bevis et al. The results presented in Ref. 2 indicate that previously unpublished bcc and bct modes should be operative in preference to the (130) mode and anomalous modes reported by Richman. In view of these results and the uncertainties involved in determining habit planes from single-surface trace analysis and twinning elements from twin-twin intersections5 a two-surface trace analysis of deformation twins in Fe-Ni and Fe-Ni-C martensites has been carried out. EXPERIMENTAL PROCEDURES Two alloys with compositions Fe-23 pct Ni-0.6 pct C and Fe-30.4 pct Ni were prepared from 4N pure materials by induction melting under a vacuum of 10"5 mm Hg. The alloys were homogenized at 1350'~ for 5 days. Both of these alloys are austenitic at room temperature with M, temperature - — 50"C. The aus-tenite grain size of the Fe-Ni-C alloy was approximately 300 to 400 p. The Fe-Ni alloy was remelted in a vertical tube furnace and the melt lowered slowly from the hot zone of the furnace to produce s ingle -crystal austenite specimens. Specimens approximately 10 by 5 by 5 mm were cut from the ingots and quenched to various temperatures below the Ms temperature. The specimens were elec-tropolished in a 10 pct perchloric acetic electrolyte before being deformed in compression at room temperature. Martensite plates which exhibited profuse deformation twinning were selected for analysis and the specimen polished on a second surface such that the two surfaces which contained the martensite plate enclosed an obtuse angle of approximately 145 deg. The specimens were then electropolished to reveal the traces of the deformation twins on both surfaces. The full orientations of the martensite crystals were determined using a divergent X-ray beam technique (Kossel line technique) employing an AEI SEM2 electron probe microanalyzer. Details of this technique which include a detailed description of the Kossel camera attachment to the microanalyzer used in the present experiments have been discussed elsewhere.3 Only additional details relevant to this investigation are discussed here. The specimens were mounted with one surface normal to the incident electron beam as illustrated schematically in Fig. 1. The martensite plates to be analyzed were located using the normal scanning equipment of the microanalyzer. The position of the electron beam and hence the position of the source of divergent X-rays generated within the crystal could be located to within 1 p. Exposure times of approximately 8 to 10 min were required for back-reflection Kossel patterns and it was found that useful diffraction patterns could be obtained consistently from heavily deformed martensite plates. A reference line (carbon contamination mark) produced on the two surfaces of the specimen by scanning the electron beam in a direction having a known relationship with the reference !ine in the X-ray camera enabled the full orientation of the crystals to be determined. Martensite plates with widths as small as 8 p could be oriented using this procedure. The Kossel line patterns were interpreted using the charts developed by Rowlands and ~evis~ as generally

Jan 1, 1969

By Edward Jeffrey

THE use of coke in metallurgy, to any important degree, dates from the middle of the 18th century. Its utilization came most opportunely for European civilization. The forests of Europe, except in the most remote and inaccessible regions, had been largely fed, in the form of charcoal, into the smelting furnaces. For a hundred years-the middle of the 17th to the middle of the 18th century-there was a stationary condition of population corresponding to the exhaustion of European forests. This situation, which was particularly evident in Great Britain, was due to the fact that the forests had been depleted and the practical utilization of coke had not begun. The coking industry is essential for our metallurgical industries, which in turn are basal to healthy economic progress. But coke is of great importance, not only on its own account, but for its byproducts, which enter fundamentally into all the arts of peace and war. The dyestuff industry and the manufacture of explosives are intimately connected with one another, as was shown by the recent war. The subject of coking coal, therefore, is well worthy the serious attention both of practical industry and the scientific investigator. The most valuable coking coals, from the metallurgical standpoint, are derived from the coals of highest ranks. Coals, for example, that have a carbon ratio of from 70 to 80 per cent. yield the most valuable coke for the blast furnace. The difficulty of investigating these coals, however, is great, for they are rather friable and delicate and possess a high carbon content, which makes them difficult to manipulate. They present, on account of their high carbon content, a considerable degree of opacity when examined, in thin sections, under the microscope. The tenderness of structure and blackness of such high-grade coking coals as those of Connellsville and the Pocahontas region make them extremely difficult to investigate.

Jan 1, 1925

By P. Martinez, A. F. Hoyte, F. E. Senftle

The possibility of applying a neutron activation technique for silver exploration is considered. A mobile positive-ion accelerator type neutron source is used to irradiate a small area of rock or soil in situ. By using a short period of irradiation and gamma ray spectral analysis, a technique is shown for silver exploration. Two different mobile units are described. Laboratory and preliminary field tests both indicate that a sensitivity of less than 1 oz of silver per ton of ore can be achieved. The increasing consumption of silver for industrial uses and also for coinage has caused a serious shortage of silver in this country. The silver shortage has been reviewed and analyzed by kiilsgaard1 who concludes that, "The best hope for meeting future demands for silver is through accelerated exploration for precious ores." As almost all the exposed "bonanza" type silver deposits evidently have been found, it is urgent that some sensitive geophysical technique be found to detect large, extended, but generally low-grade, secondary ores, as well as hidden vein deposits. Silver is easily made radioactive by exposure to slow neutrons; hence a neutron activation method appears promising for locating silver deposits. The principles of mineral beneficiation using neutron activation techniques were discussed some years ago.2-4 Using the same approach, a preliminary description5 has been published of neutron activation as a mineral exploration tool. An exploration technique is described in which silver is made radioactive in situ and detected with a gamma radiation counter. The technique is similar to the well-known method used for uranium exploration. THEORETICAL CONSIDERATIONS Elemental silver consists of two isotopes, Ag107 and Ag109, having naturally occurring isotopic abundances of 51.4% and 48.6%, respectively. For short periods of irradiation of silver by thermal neutrons, the long-lived 250 day, half-life isotope, Ag110m, is not produced in significant quantities. However, significant quantities of 2.3 min half-life Ag108 and 24.5 sec half-life Agl10 are formed by the following reactions. Ag108 and Agl10 emit a 0.44 Mev (million electron volts) and a 0.66 Mev gamma ray, respectively. Ag107 + n + Ag108 (2.3 min) Ag109 + n + Ag110 (24.5 sec). Because of the large capture cross section (110 barns) of Ag109, and short half-life of Ag110 (24.5 sec), the 0.66-Mev gamma ray is the most prominent emission from silver for neutron activation periods of about a minute's duration.* The 0.44-Mev gamma ray from Ag108 will also be present, but will be one or two orders of magnitude lower in intensity. The decay scheme of Ag110 is shown in Fig. 1. If the neutron irradiation time is limited to about 100 sec, the Ag110 activity will essentially reach saturation and can be used to detect the presence of silver. In a neutron flux of 10 8 neutrons/cm2/set, the induced 0.66-Mev activity in 1 g of silver will be about 2 x 107 disintegrations per sec. This is about 1000 times the measurable gamma activity of 1 g of uranium in equilibrium with all its decay products; hence there is ample activity for detection. Under the same conditions of activation, most of the other elements do not reach this relatively high disintegration rate. Although this is in favor of the proposed technique, other problems must be considered. For mobile operation, it is desirable to obtain the largest neutron flux to weight ratio. Hence we have used a small 150-kev accelerator-type neutron source rather than an isotopic source such as an americium-beryllium neutron source. By use of remote control system, an accelerator-type neutron source can be safely used without the massive shield required for an isotopic source. Moreover, an accelerator-type source is more versatile in that it allows one to use a flux of either 14-Mev or 3-Mev neutrons, depending on whether a tritium or a deuterium target is used. With a 14-Mev generator, one can obtain a flux of 10 9 neutrons/cm 2/sec, and with a 3-Mev generator, the flux is generally two orders of magnitude less. Although silver will become activated with either generator using proper moderation, detection may be

Jan 1, 1968

By G. H. Matheson, J. M. W. Mackenzie

The flotation rate of coal has been studied using a continuous laboratory flotation cell and a multiple exposure photographic technique. The effects of particle size, reagent additions and cell turbulence on the flotation rate of coal have been investigated. The results have been analyzed in terms of current theories of particle bubble encounter and adhesion. The rupture forces which occur during particle bubble encounter have been shown to have an important effect on the flotation rate of coarse coal particles. The flotation of coal is a time dependent process, and in order to obtain a complete understanding of the operation it is necessary to determine the kinetics of the process. In coal flotation, the flotation rate and the associated values of cell productivity in terms of tons per kilowatt-hour and tons per cubic foot of cell volume are of greater importance than in most other mineral flotation operations. The reasons for this are associated with the low unit value of coal and the relatively high cost of coal flotation compared with other coal cleaning processes. An important aspect of coal flotation kinetics is the design of coal flotation cells. The cells used in many coal cleaning operations are often replicas of those used for the treatment of sulfide ores and are not necessarily suitable for the treatment of coal washing pulps, which usually contain a higher percentage of coarse and floatable material than the sulfide pulps for which the cells were designed. This disadvantage of many coal flotation cells has been recognized by Russian engineers who, by the addition of baffles to their subaeration coal flotation cells have increased the cell capacity by 100%. Investigation of the variables which influence flotation kinetics and cell productivity are, therefore, important to the coal industry where flotation is the only accepted method of cleaning the fine (-1/2mm) coal. The kinetics of the flotation process have been investigated in detail by Schumann10 who developed a continuous flotation cell which permitted the study of flotation under steady state conditions. This technique has been used by Gaudin et a1.,6 Brown and Smith and recently by Jowett and Savfi.7 The latter authors have developed a refined mathematical treatment for interpreting the results of continuous laboratory tests. Attempts have also been made to study flotation kinetics using conventional batch testing techniques. The experimental difficulties, however, and the problems of determining the order of the flotation rate process have made this technique of dubious value. A summary of the proposed rate equations for batch testing and the difficulties associated with this technique is given by Brown and Smith. 2 The experimental techniques described above are concerned with the rate of production of froth product. However, several authors, notably Sutherland, 11 Bogdanov1 and Philippoff, 9 have analyzed flotation

Jan 1, 1963

By T. Lane Carter

It is a curious fact that while in our Transactions there are papers dealing with mining-districts in all parts of the world, in Europe, Asia, Africa, and Australia, there is not one which describes the mining possibilities of Nicaragua, our near neighbor. To be most interested in distant objects, like the moon, and to neglect what lies at our feet, appears to be a trait of human nature. The neglect of Nicaragua is not confined to the American Institute of Mining Engineers. In no other transactions am I able to find papers dealing with mining in Nicaragua, some parts of which are as much in need of discovery and research as the North Pole. I hope this paper will be the precursor of many others to be printed in our Transaclions, dealing not only with the miniilg possibilities of Nicaragua, but with the whole of Central America, where there are vast areas a,waiting skill and capital for their development. Much of this capital and skill should come from the United States in the future, although it is probable that European capitalists, when they appreciate fully the possibilities, will investigate more and more the mining-resources of Nicaragua and ot'her Central American republics. Fig. 1 is a sketch-map of Nicaragua showing the principal mining-districts. 11. History. Mining in Nicaragua did not begin yesterday. It was commenced by civilized man when the Spanish conquerors pene-' trated into the interior and forced the natives to procure the precious metal for them. It is strange that the Spaniards did not find more gold, and work on a scale as extensive as in Colombia and other parts of South America. Probably in Nicaragua the Indians covered up most of the rich prospects

Jan 1, 1911

By George A. Guess

THE increasing demand for greater speed and more accuracy, in making daily assays of ores and products from mills treating material containing but very small quantities of lead and copper, has caused the older analytical methods to be supplanted by new ones devised to meet the needs of modern work. For " control " work in copper analyses, I had, previous to the present equipment, introduced in my laboratory the ordinary electrolytic method, using hollow cylindrical electrodes, and with these I began a series of experiments in determining the lead-content of daily mill-samples and controls. The results, proving accurate and satisfactory, I then devised, with Mr. H. E. T. Haultain, a cheaper electrode than the ordinary jacket electrode, which costs from $15 to $20,-the expense of the older form making the installation of many units very costly. The form of cathode finally adopted as the most satisfactory, shown in Fig. 1, is cut from 0.001-in. platinum foil. It is 12.5 cm. long, and is divided into a blade 4 cm. wide and 6.25 cm. long, and a tongue 0.7 cm. wide and 6.25 long, the immersion area being 50 sq. cm. and weight 1.5 grams. The blade is first sand-blasted and then corrugated lengthwise, in order to impart the necessary rigidity. Strips of platinum foil 0.001 in. thick, 12.5 cm. long and 0.5 cm. wide, having a median corrugation, form the anodes. Three electrodes are used in each cell, one anode in the middle and one cathode oil each side of the anode. These electrodes are connected to slotted alumi¬num terminals, in which they are held by contact pressure. The terminals are -in. rods, projecting 2 in. horizontally in front of the wall of the cabinet.; at the back the middle electrode (anode) is connected with one pole of the current, and the two outer ones (cathodes) with the other pole.

Nov 1, 1905

By Sherwin Kelly

IN presenting this brief historical perspective, it is not my purpose to address myself to the geophysicists, to most of whom the story is already well known. My objective is to draw the attention of those who hold the belief that geophysics is something new, typically twentieth century, to the fact that fundamentally, whether it was known by the name of geo-physics or not, the science is an ancient and an honorable one. It began many centuries ago, and our modern civilization and its commerce owe a great debt to its founders, who today are likely to he overlooked and their names forgotten. The word "geophysics" means the physics of the earth, and is descriptive of a science that in many ways bears the same relationship to geology that astrophysics does to astronomy. When dealing with dis-tant stars or deeply buried rocks, the experimenter cannot reach them to obtain samples, which can be taken to his laboratory for study. He therefore exhibits the resourcefulness of Mahomet in the mountain episode, and makes the terrestrial globe or the cosmic universe his labora-tory, studying the effects of distant bodies on certain "fields of force"" which come to him across interstellar space, or through the rocks that make our earth. The application of these techniques of the physics laboratory to the study of the stars is the science of astrophysics, and to the investigation of the earth is geophysics. Yet the origin of the most valuable contribution to the world's trade and commerce ever made by geophysics remains lost in deep obscurity. Unknown even is the country wherein lived the unsung genius who invented the first geophysical instrument, the mariner's compass! Worse yet, it is not certain whether this invaluable guide of man had its begin-nings in Europe or in Asia. A Chinese legend tells of the Emperor Hwang-ti, who attacked his enemy Tchi-yeou on the plains of Tchou-lou in the year 2634 B.C., whereupon the latter magically raised such a fog that the Emperor could not pursue the retreating troops. Not to be outdone, the mighty ruler constructed a chariot that indicated the cardi-

Jan 1, 1938

By T. E. Leontis

The importance of magnesium alloys in the manufacture of aircraft engines has been realized for many years. A concentrated effort has been exerted in the laboratories of the Dow Chemical Co. to develop magnesium-base alloys with improved properties at elevated temperatures whereby greater advantage can be taken of the inherent lightness of these materials. In an earlier publication, attention was called to the superior tensile properties and resistance to creep of cerium-containing magnesium alloys at temperatures up to 700°F. More recently, additional data on magnesium-cerium alloys have been furnished by Murphy and Payne. The present paper deals with the mechanical properties of sand-cast magnesium alloys containing zinc, at temperatures up to 500°F. The study includes binary Mg-Znt alloys containing up to 10 pct zinc and several ternary and some polynary alloys based on the Mg-~Zn,f Mg-jZn, Mg-4.4211, Mg-6Zn, and Mg-roZn binaries. The compositional variation in the tensile properties, hardness, and creep at room and elevated temperatures, and in the electrical conductivity at room temperature has been determined. The results of these tests show that many zinc-containing magnesium alloys exhibit resistance to creep at elevated temperatures significantly higher than that of present commercial magnesium alloys, but lower than that of alloys of the magnesium-cerium type. In addition, they have high tensile properties at room and elevated temperatures and high conductivity. This combination of mechanical properties and conductivity indicates that these alloys should be given serious consideration for commercial applications involving exposure to temperatures higher than those to which present commercial magnesium alloys can be taken safely. Literature The properties of sand-cast magnesium alloys containing zinc as a principal alloying element have not been investigated very extensively, especially at elevated temperatures. The following remarks, which are confined to sand-cast alloys, will serve as a summary of the most important references on this phase of magnesium metallurgy. The first recorded determination of the tensile strength of binary Mg-Zn alloys as a function of zinc content was reported by Aitchison. Similar studies, including the measurement of elongation and hardness, have been performed by Gann and Winston,' Dumas and Rockaert, Haugh-ton and Prytherch,6 and by Spitaler, the last being reported by Beck.' A slight superiority in the tensile strength of chill-cent Mg + 8 es alloy Over the sand-cast alloy was noted by Maybrey.8 That alloys of magnesium containing 5 to 12 pct zinc

Jan 1, 1949

By L. W. Legerwood

During the past three decades, the oil industry has expended increasing eflorts seeking improved drilling tools or systems to reduce drilling costs. The total cost of these efforts is unknown, but it certainly amounts 10 tens of millions of dollars. Most of the "new" system that past and present investigators have sought to develop actually are old public information. In seeking to implement new-systern concepts, investigators have tested the following: impact at frequencies ranging from 6 to 300 cycles per second; electrical, mechanical and hydraulic meam of actuating percussors; bit rotary speeds up to 2,000 rpm; electric and hydraulic bottom-hole means of rotating bits; bottom-hole machines with power outputs up to 400 hp; shock waves; explosives; high-velocity pellets; flame; arc; grinding wheels; abrasive jets; erosion by high-velocity gases; chemical attack; electric current; magnetic waves; retractable rock bits; reelable drill pipe; continuous coring with reverse circulation; and automation of drilling rigs. Table I shows how these investigations are grouped for discussion purposes in this paper. In spite of these efforts to discover new and improved systems, rotary drilling main;aim its economic leadership. Undoubtedly, rotary drilling costs will continue to be reduced by rigid application of the best available technology and by development of new rotary technology. In view of the extensive past development programs, however, significant long-range improvement appears to be a research, not a development problem. Research must postulate and prove theories and principles governing variour subsurface rock-failure processes pertinent to both rotary and new systems. Ah, research must produce physical and engineering data relative to these processes. When such information is available, earth boring will graduate from an art to a science. Major improvements in rotary drilling can then be expected, and the systematic evolution of an improved drilling method can be initiated—with a strong probability for success. Development of drilling methods other than rotary drilling has been one approach investigated by the industry as a means for reducing drilling costs. Major cost-reduction efforts, however, have been centered on engineering development work aimed at incremental improvements in rotary drilling. A relatively minor effort has been expended to establish basic physical principles and engineering data pertaining to the earth-boring process which can serve as a foundation for the development of cost-cutting drilling hardware. Current oil-industry economic trends have added impetus to the need for effective programs to reduce drilling costs. However, areas for expanded future efforts should be selected only after careful study of past investigations. It is the purpose of this paper to review past and Dresent industry efforts to develop new drilling tools or systems and to suggest areas where additional science is needed. Past reviews of drilling methods have been limited to a few processes prominent at the time the reviews were made. This paper seeks to present a concise, well organized review of all methods that have received actual development or test work. The preparation of a paper seeking to review all past developments is fraught with many difficulties, not the least of which are errors in or obsolesence of printed matter used as source material and the lack of data on industry developments which have not been published. Since de-

By M. R. Geer, H. F. Yancey

With the exception of pneumatic processes and a few special beneficiation methods of comparatively limited application, all mechanical coal-cleaning and mineral-dressing processes involve the admixture of solid particles with a liquid, generally water. Upon completion of the beneficia-tion process the solids must be reclaimed from the water. With coarse particles separation of solids from water is accomplished readily by the simple expedient of screening, but recovery of fine solids presents a much more difficult problem. Thickening and dewatering are practiced so generally, both within the mineral industry and elsewhere, that they have been the subject of study through the years and a number of processes for making the solid-liquid separation have been developed. Dorr-type thickeners have been standard equipment lor many years, and more recently driers employing centrifugal force have gained in popularity.' A cyclone device employed to thicken the loess suspension is a novel feature of the loess heavy-medium coal-cleaning process developed by the Netherlands State Mines in the thirties. The cyclone thickener was first mentioned by Driessen2 in 1939 in a paper describing the loess process and has been the subject of two more recent reports by the same author.3 The cyclone does not differ greatly from cyclone dust collectors used in this country for years, except that it is operated wet rather than dry. Advantages of the cyclone over other thickening devices are its simplicity of construction, high capacity, and the fact that, having no moving parts, it is simple and inexpensive to operate. The Bureau of Mines became interested in the cyclone after one of the present authors observed it in operation in the Netherlands in 1945. The first experimental work with the cyclone conducted by the Bureau of Mines was an investigation of the unit functioning as a heavy-medium cleaner for fine coal—a use for the cyclone that was conceived long after it had been perfected as a thickener. The results of this investigation were published last year.4 The present investigation deals exclusively with operation of the cyclone as a thickener. Object and Scope of Investigation Although the cyclone thickener has been dealt with in three reports by Driessen, its use as a thickener was not the principal subject of any of these reports and therefore neither the cyclone itself nor its operation was described completely. The design of the cyclone was described only in a very general way, only limited operating results were given, and virtually nothing was disclosed about the influence of the various possible operating variables. Moreover, the Netherlanders apparently had employed the cyclone exclusively for thickening loess and had not employed it On coal 'lurries. One English colliery has used a cyclone to thicken coal slurry,5 and as it appeared that

Jan 1, 1949

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1'2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1'2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940

By NEWTON B. KNOX

PERU, lying south of Ecuador and having common frontiers with Brazil, Chile, and Bolivia, includes over a thousand miles of the Andean mountains. The coastal plain is arid and narrow and the Amazonian jungle region is of interest only on account of its oil and gold placer possibilities. The mountain zone, however, here forms one of the world's most highly mineralized regions. The Peruvian Andes, like their Bolivian and Ecuadorian counterparts, form two distinct chains separated by the great Apurimac and Maralion valleys; but these rivers cut through the Eastern range to join the Amazon drainage, and the central valley is missing north of the passes thus formed by these rivers; the localities where the ranges are joined are aptly called knots. In addition, in central Peru, there exists a third range lying to the east of the first two and separated from them by the Urubamba and Huallaga Rivers. The Eastern range, however, is of little importance to the miner for few metal deposits are to be found therein except for the gold mineralization in the South. In general, deposition of metals in the Peruvian Andes accompanied igneous intrusions which invaded the folded Paleozoic and Mesozoic rocks during the Tertiary; thus the ore bodies are all typical of shallow or moderate depths.

Jan 1, 1945

By A. B. Cox, L. W. Wark

In an earlier paper1 measurements of contact angles due to the effect of xanthates on mineral surfaces were reported. The solutions in which these measurements were made differed widely from those of modern flotation circuits. It is intended, however, by introducing, one at a time, the other principal reagents of flotation, to approach gradually the solution composition of flotation liquors. The work now described is an attempt to determine the effect of one of the most important of these reagents—namely, sodium cyanide—on the establishment of air-mineral contact. The work has been carried out for the following companies: Broken Hill South, North Broken Hill, Zinc Corporation, Electrolytic Zinc of Australasia, Mount Lyell Mining and Railway, and Burma Corporation. Since the effect of cyanide is inseparably connected with the alkalinity, the results cited below deal with the mutual effects of alkalis and cyanide. Alkalis alone exert a significant effect on the air-mineral contact but comparatively large amounts are required. Since the addition of a small amount of cyanide greatly decreases the degree of alkalinity necessary for the suppression of contact at surfaces of any of the minerals experimented with (except galena) and since alkalis are rarely used alone in practice, little attention has been paid to cyanide-free solutions. It was shown in the previous paper that, excluding the dixanthogen effect, whenever contact was practicable at all in an ethyl xanthate solution the angle of contact was 60". There is, therefore, less necessity to measure equilibrium contact angles; in fact, the experiments herein described have generally been conducted with a view to determining whether contact is possible and not to measuring the actual value of the contact angle. The separations which have generally to be effected in dealing with complex sulfide ores are: (1) galena from sphalerite, pyrite, etc.; (2) sphalerite from pyrite and/or gangue minerals; (3) copper minerals from pyrite and gangue minerals; (4) pyrite from gangue minerals; (5) chal-

Jan 1, 1935