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By J. H. Schulman, M. H. Buckenham

Although much interest has been taken in the use of mixed collectors in flotation, this investigation is probably the first in which oppositely charged collectors have been considered. The results obtained and the techniques used could well be applied in the behavior of other mixe the behavior of other mixed collector systems and could possibly explain the effective flotation results which have been reported when various collector combinations have been used. Collectors conventionally employed in flotation systems are soluble in water, but many of their homologs of longer hydrocarbon chain length are insoluble. The properties and behavior of these insoluble compounds may be conveniently studied when they are spread as monolayers at the air/water interface on the Langmuir-Adam trough. Although some extrapolation is involved in applying effects observed at this interface to the solid/liquid interface where the action of collectors is most important in flotation, the technique nevertheless is most useful for the study and interpretation of flotation phenomena. Of particular interest in this field are investigations on the insoluble monolayers of the fatty acids, alkyl sulfates and alkyl amines; the penetration of these insoluble monolayers by soluble surface active components and their interaction with metal ions from the underlying solution.'-' Unfortunately, the insoluble xanthates and related compounds do not exhibit stable monolayer properties due to rapid oxidation at the air/water interface and, therefore, cannot be studied directly in this way. These approaches have enabled Leja and Schulman8 to suggest mechanisms explaining dynamic attachment of mineral particles to air bubbles involving collector-frother interaction and the adsorption of collectors onto mineral surfaces. In this and other papers 9-12 considerable evidence is presented to support the concept of collector-frother and metal ion-monolayer interaction and to emphasize the value of monolayer techniques in elucidating the flotation system. Molecular interactions resulting from monolayer penetration are determined by the nature of and the association between both the polar and nonpolar groups of the two molecules concerned. Stable complexes are formed on penetration when interaction takes place between both the polar and nonpolar groups, and although the resultant complexes are not necessarily true chemical compounds, the properties of the molecularly associated complexes are very different from those of the individual components. Shortening of, or changes from, a straight hydrocarbon chain in one of the reacting molecules reduces considerably the stability of the associated complex as do changes in temperature, pH and substrate composition. The effect of hydrocarbon chain length becomes most important when observed effects are to be applied in flotation studies where soluble homo-logs and, therefore, much shorter hydrocarbon chain lengths are used. The present investigation is based on Langmuir trough work carried out by Bowcott,l3 who studied the penetration of insoluble amine monolayers by potassium lauryl xanthate. Bowcott observed that cetyl amine monolayers were readily penetrated by xanthate, but found that with time the high film pressures resulting from penetration and association fell off, indicating decomposition and ejection of xanthate from the film. This decomposition was pH dependent. Of particular interest in this work were studies on an equimolecular mixed monolayer of the fully N-substituted ammonium compound, for example, cetyl trimethyl ammonium iodide (CTAI) and potassium cetyl xanthate. Despite the fact that the CTAI is water soluble and the xanthate on its own is incapable of forming a monolayer, the mixed film was stable up to a surface pressure of 67 dynes per cm. In this condensed state the xanthate was stabilized against atmospheric oxidation, although iodine injected beneath the film caused an immediate collapse. The stabilizing of xanthate against oxidation by association with an alkyl trimethyl ammonium bromide (TAB) could be important in flotation, and a study of the performance and behavior of mixed collectors therefore was undertaken. A modified Hallimond tube operated under controlled conditions was used to evaluate flotation. Surface tension measurements were made to investigate the properties of the soluble

Jan 1, 1963

By M. M. Botz, F. W. DeVries

Discussion by F.W. DeVries Comments on natural cyanide attenuation. The paper by Botz and Mudder in the November 2000 issue of Minerals and Metallurgical Processing had one disappointing aspect. Table 1 (p. 229) failed to include a significant species - neutral copper cyanide (CuCN). This compound has been most trouble-some in many plant-scale cyanide cleanup processes, includ- ing acidification-volatilization- reneutralization (AVR), hy- drogen peroxide cleanup and air/SO2 cleanup. It has also plagued many pilot efforts to use ion-exchange (IX) resin technology. This author elucidated the concept that, under some conditions, copper cyanide failed to precipitate out of treated effluents and appeared to exist as a filterable colloid that reported as copper and cyanide, with the latter measured as WAD (weak-acid-dissociable) cyanide in that analytical method. The concentrations measured were very near the levels of 0.2 ppm, often the regulatory limit for WAD cyanide. The copper concentration, using the 1 : 1 ratio for this com- pound, would then be more than 0.4 ppm, which could also be unacceptable. We discovered that it was unsafe to assume that the Cu(CN),- would surrender both cyanide ions simultaneously and allow cupric copper to be removed subsequently as, say, cupric ferrocyanide (Hatchett's Brown). This compound could be ignored as safely as the "iron blues," as essentially an inert solid, stable in geologic time if not exposed to sunlight. Under poorly controlled oxidation of the cyanocuprite ions (copper with four, three or two cyanides complexed to the copper), CuCN could well be formed and could not be assumed to precipitate out as a solid. The authors of the paper, by failing to include the CuCN species in their model, may have left users of the model prone to ignore the possible occurrence of the colloidal(?) form in the discharge, thus finding an effluent that failed to meet regulatory limits. (See addendum below.) This somewhat ephemeral material may well have been responsible for some large-scale failures of cyanide destruction technology to succeed at sites in North America and elsewhere. Two specific references alluding to this occurrence may be found: Griffiths et al., 1987, "The detoxification of gold-mill tailings with hydrogen peroxide," Journal of the South African Institute of Mining and Metallurgy, September, p. 282. DeVries, 1989, "Improved understanding in detoxification of cyanide leach liquors using peroxide" Rand01 Gold Conference, Sacramento CA, p. 15 1. It is advisable for workers in this area of cyanide removal or recycle to avoid assuming that CuCN will, with certainty, precipitate out of solution, or that the dicyanocuprite ion will part simultaneously with both cyanide ions and allow cupric copper to be dealt with by other reactions. One further piece of work may be incomplete. That is, a definitive study of the long-term behavior of CuCN that does precipitate when exposed to other compounds present in neutralized tailings. Addendum. The extremely complex reaction of cupric ion on cyanide- which, of course, results in oxidation of cyanide to cyanate, probably through the intermediate stage of forming cyanogen [(CN)2] from oxidation of HCN with its hydrolysis to cyanate and cyanide ion - involves two cyanide moieties and the reduction of the cupric ion back again to the cuprous state. This, then, can form the CuCN potential "solid" that was already the undesirable species. In cyanide cleanup, with either air/SO2 or hydrogen peroxide, copper is generally employed as the catalyst, so it is unclear what happens when the CU(CN)2-1 is ultimately exhausted. Certainly, the field evidence is quite clear that all

Jan 1, 2002

Question 1—1s Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions. Especially in Limestone or Other Dense Rocks Discussion by: A. M. Bateman.........120 S. F. Kelly........... 125 C. H. Behre. Jr........118.123 G. B. Langford......... 123 T. M. Broderick.........121 H. E. McKinstry......... 116 R. H. Clarke.......... 123 D. H. McLaughlin........ 118 J. D. Forrester for M. H. Gidel . . 11.4 W. H. Newhouse......... 123 G. M. Fowler......112. 116. 121 R. H. Sales.......... 116 L. C. Graton..........121 Edward Sampson......... 122 R. D. Hoffman.........120 J. 8. Stevenson.......... 117 I. B. Joralemon.........121 L.B.Wright........... 112 Question 2—What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? Drscussion by: G. W. Bain....... 127 G. M. Fowler....... 131 C. H. Behre, Jr. ..... 131 L. C. Graton....... 128 J. S. Brown. ...... 126 G.. F. Loughlin...... 128 E. L. Bruce ....... 129 R. H. Sales........ 129 R. H. Clarke...... 130 A. K. Snelgrove....... 130 Question 3—Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? Discussion by: J. M. Boutwell...... 139 G. B. Langford..... 139 T. M. Broderick..... 138 . G. F. Loughlin...... 135 E. Y. Dougherty..... 137 R. H. Sales...... . 134 G. M. Fowler....... 132 F. A. Thomson..... 136 I. B. Joralcmon...... 132 Edward Wisser:..... 140 General s. F. Kelly................. . ...........145 References...............................146

Jan 1, 1941

Question 1—1s Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions. Especially in Limestone or Other Dense Rocks Discussion by: A. M. Bateman.........120 S. F. Kelly........... 125 C. H. Behre. Jr........118.123 G. B. Langford......... 123 T. M. Broderick.........121 H. E. McKinstry......... 116 R. H. Clarke.......... 123 D. H. McLaughlin........ 118 J. D. Forrester for M. H. Gidel . . 11.4 W. H. Newhouse......... 123 G. M. Fowler......112. 116. 121 R. H. Sales.......... 116 L. C. Graton..........121 Edward Sampson......... 122 R. D. Hoffman.........120 J. 8. Stevenson.......... 117 I. B. Joralemon.........121 L.B.Wright........... 112 Question 2—What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? Drscussion by: G. W. Bain....... 127 G. M. Fowler....... 131 C. H. Behre, Jr. ..... 131 L. C. Graton....... 128 J. S. Brown. ...... 126 G.. F. Loughlin...... 128 E. L. Bruce ....... 129 R. H. Sales........ 129 R. H. Clarke...... 130 A. K. Snelgrove....... 130 Question 3—Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? Discussion by: J. M. Boutwell...... 139 G. B. Langford..... 139 T. M. Broderick..... 138 . G. F. Loughlin...... 135 E. Y. Dougherty..... 137 R. H. Sales...... . 134 G. M. Fowler....... 132 F. A. Thomson..... 136 I. B. Joralcmon...... 132 Edward Wisser:..... 140 General s. F. Kelly................. . ...........145 References...............................146

Jan 1, 1941

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.' It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

By R. F. Mehl, M. L. Swanson, J. P. Hirth, G. M. Pound

The sorption of zinc in a-brass was investigated. By analyzing the elliPtically polarized light reflected from the surfaces of a-brass solid-vapor couples, their optical constants and surface compositions were determined. It was shown that the surface compositions approached an equilibrium value exponentially with time. The bulk diffusion coefficient, surface diffusion coefficient and condensation coefficient for a-brass solid-vapor couples were calculated near 350°C from the experimental results. It has been assumed during various diffusion experiments with bimetallic solid-vapor couples (Dunn,1 Seith and Kraus,2 Jenkins,3 Balluffi and Seigle,4 and others) that the surface composition of such couples reaches its equilibrium value immediately. Although this assumption is probably valid at elevated temperatures, it is certainly not expected to be confirmed at lower temperatures.* consequently, it was decided that a fundamental experiment, designed to solve this problem as well as to examine all aspects of bimetallic sorption, would be the investigation of the rate of approach to equilibrium of the surface composition of solid-vapor couples. The sorption (i.e., adsorption, absorption, and desorption) of metals is obviously dependent on the state of the metallic surface and substrate. Much recent theoretical8"9 and experimental10-12 work on condensation and evaporation of pure metals has shown that the surface contour in atomic dimensions is a critical factor in sorption, so that any deformation or contamination13,14 of the surface exerts a profound influence. It is also known that absorption or diffusion occurs much more rapidly along grain were and in other deformed regions. Thus an effective sorption experiment must utilize a strain-free and clean surface, or at least a clearly defined and reproducible surface state. A mechanically polished surface is in a highly deformed17-l9 state. Because the degree of this deformation is uncertain, it is clear that for most experimental purposes a strain-free (i.e., etched, chemically polished, or electropolished) surface is desirable. Although adsorbed gas molecules on metallic surfaces are unavoidable even in the highest vacuum,20 oxide films can in some cases be removed by suitable vacuum annealing. Electrolytically polished and annealed surfaces, being relatively without strain, smooth and free of bulk oxides, were considered adequate for the present sorption experiments. Measurement of the surface composition of a solid-vapor couple presents a unique problem. Since experiments to determine the approach to equilibrium of the surface composition must be performed at temperatures where diffusion is very slow, solute penetration is so small that conventional analytical methods are unsuitable. An optical reflectivity method utilizing a polarization spectroscope was employed because of the relatively small penetration (~200A) of visible light in metals. By this method, elliptically polarized light reflected from the metal surface was analyzed and compared with that reflected from samples of known composition. The a phase of the copper-zinc system was

Jan 1, 1962

Upon subduction, water is liberated from the sediments and the porous struc- ture of the oceanic crust and from de- hydration of minerals for redistribution and chemical reaction. A survey of pro- cesses which are likely to occur along the subducting plate reveals that water may well be basic in subduction induced gas generation, magma formation and ore deposition. In analogy to the industrial water gas process, reaction of water with car- bonaceous matter, in subducted sediments is likely to yield substantial volumes of hydrogen and carbon dioxide. While water and carbon dioxide appear to play a determining role in the development of differentiated magmas, hydrogen will react with metal sulfides and sulfur to form hydrogen sulfide which is essential in sulfide ore depo- sition. A survey of possible metal extrac- tion chemistry along subduction suggests a stepwise solubilization of metals from sediments and oceanic crust, and a poten tial accumulation of dissolved metals in zones of characteristic composition. The metal spectrum in ore deposits at near surface appears to reflect the com- position of the solution in the respec- tive subduction zone. A tendency for preferential solubi- lization of copper at subductidn level, from among the transition metals, an in- creasing generation of hydrogen sulfide in the sane direction and partition effects as well as sulfide precipitation characteristics lead to enrichment in copper and to its selective deposition in the direction towards the trench as observed in S. Latin America. A postscript deals with the formation of native copper.

Jan 1, 1986

Geophysics is playing an increasingly important role in the exploration industry. In the soft rock scene the application of seismic techniques is basically mandatory prior to any drilling program. Simply, this is because, in a majority of situations, the seismic method is ideally suited to mapping accurately relatively flat lying strata and displaying structures that may host oil or gas. It is worth stressing that seismic methods do not delineate oil or gas but they map well in two or three dimensions. In the base metal arena, geophysical methods used are generally focussed on direct detection methods with the mapping application not often used except in potential fields (magnetics and gravity). The success rate in the last decade has not been good but this does not only apply to the application of geophysics; it really applies across the board of exploration techniques. Both geological and geochemical exploration have not had a success rate commensurate with the funds injected. Basically in the last ten years we have failed as explorers! As explorers we have been negligent in mapping. As geoscientists we have let the basic mapping and observation skills diminish û the old adage æboots on the groundÆ is still applicable but are we doing enough of it? The answer is clearly no. As explorers the huge burden of bureaucracy, eg Government Acts û local, state and federal, safety compliance, environmental compliance, etc has reduced the ægeologicalÆ time dramatically. This has culminated in an over-reliance on quick fix solutions, eg spot the bump geophysics or geochemistry. This obviously simplistic scenario is arguable but there is no doubt in the geoscientific areas we have failed in the last decade to provide adequate geoscientific maps to assist in exploration. This failure could partially be responsible for the current demise of the industry resulting in a reduction in exploration dollars and, hence, people. This trend is seen acutely in the geophysical area where the head count in comparison with the geological fraternity is low. Other trends during this downturn are inevitable as explorers maximise the use of the dollar in exploration and diminish spending on advances in geophysics. Improvements are being seen however in geophysical equipment, although it is considered that the main improvement will be in the interpretation of data. Specifically, the trend will be towards integrating geophysical data into geological, geochemical and spatial data sets producing quality interpretation and providing low risk drill targets. Examples of the current trends in hardware and future directions are discussed below. In interpretive schemes there are very few examples of integrated interpretation but the possible trends will be discussed with limited examples.

Jan 1, 2000

By R. W. Fountain, John Chipman

The solubility of nitrogen in Fe-B alloys (0.001 to 0.91 pet B) is determined by the Sieverts' technique for temperatures of 950° to 1150°C. The activity coefficient of nitrogen is decreased by boron. The three-phase equilibrium between ? iron, BN, and gas is established and also the four-phase equilibrium between iron, BN, Fe2B, and gas. The above equilibria are calculated for a iron. The relation of these data to hardenability and strain aging of boron-treated steels is discussed. BORON additions are known to enhanbe the hardenability of heat-treatable steels and to assist in the control of strain aging in sheet steel for deep drawing. The increase in hardenability is explained by the theory that adsorption of boron on austenite grain boundaries reduces their free energy and thus retards ferrite and upper bainite nucleation.l,2 Digges and Reinhart3 have shown that the full effectiveness of boron in commercial steels is achieved only when strong nitride formers such as titanium and zirconium are also present. The influence of nitrogen on eliminating the boron contribution to hardenability was also demonstrated by Shyne and Morgan.4 These workers prepared Ni-Mo steels containing either nitrogen or boron or nitrogen plus boron. The nitrogen-plus-boron steels showed the lowest hardenability which was attributed to the presence of stable nucleating particles, presumably nitride. Morgan and Shyne5-7 have shown that boron in the amount of 0.007 pet will completely eliminate strain aging due to nitrogen in low-carbon, open-hearth steels. In addition, by proper control of the boron additions, a rimming steel can be produced. Since the effectiveness of boron on hardenability and eliminating strain aging is influenced by the amount and distribution of the nitrogen in the steel, the present study was. undertaken to determine the influence of boron on the solubility of nitrogen in iron. EXPERIMENTAL PROCEDURE The solubility of nitrogen in Fe-B alloys was measured by the method of Sieverts, which consists of determining the amount of gas dissolved by the metal in a constant volume system. The apparatus employed in this investigation and the experimental details have beendescribed previously.B AMcLeodgage was added to the apparatus to allow measurements at very low pressures. The alloys were melted at reduced pressure in a basic-lined induction furnace using electrolytic iron and ferroboron. Ferroboron was added after the primary deoxidation of the iron with carbon. Since it was difficult to attain a constant low level of oxygen by this procedure, silicon was added after the carbon deoxidation and prior to the ferr obor on addition. The alloys were castas 2-in. sq ingots, heated in argon at 1050loC, and forged to 1/4-in. plate. After forging, 1116 in. was machined from each side of the plate to remove any possible contamination, and it was then cold-rolled to 0.010-in. sheet. The sheet was cut into approximately 1/4-in. squares and pickled in an inhibited H2SO4 solution to ensure a clean surface. In the case of the boron alloys, a hydrogen treatment could not be used for surface cleaning because boron losses resulted. The composition of the alloys is given in Table I. For a solubility determination, a 75-g sample was inserted in a quartz tube and sealed in place in the apparatus. The entire system was evacuated at room temperature and leak tested for 24 hr. If no leaks were observed, the system was heated to the temperature of measurement and again leak tested for 24 hr. If no leaks were detected, the hot volume and solubility determinations were begun. The hot volume was determined at a constant temperature for each run by admitting successive amounts of argon and recording pressure vs volume, which, in all cases, resulted in a straightline relationship. The argon was then removed and the procedure repeated with nitrogen. Successive additions were made until the desired nitrogen content of the metal and equilibrium pressure of the system were obtained. The

Jan 1, 1962

By H. J. McQueen, G. C. Kuczynski

ThE useful properties of k6-Alfenol and the thermenol alloys (summarized by J. E. Nachman and W. J. Buehler') have encouraged research into those alloys which, having compositions near 25 at. pct Al, 75 at. pct Fe, undergo an ordering transformation between 500° and 550°C. The equilibrium diagram of the iron-rich iron-aluminum alloys was first determined by Bradley and Jay.2,3 They distinguished three structures: the disordered, which is bcc; FeAl, which is simple cubic with one Fe atom and one Al atom per lattice site; and Fe3Al, which is fcc with three Fe atoms and one Al atom per lattice site. This last structure may be conceived as eight body-centered cubes with Al atoms at the centers of alternate ones, so that Al atoms have only Fe as first and second nearest neighbors. Later, Osawa and Murata4 determined the boundaries of the different superlattice regions in the iron-rich Fe-Al solid solution by dilatometric and X-ray methods. Two of the six phases, which they found between 0 and 50 at. pct Al, were never identified by other workers. A. Taylor and R. M. ones,' concurrently with and independently of this research, redetermined this diagram by measuring lattice parameters at temperature. Further reference will be made to their results. EQUILIBRIUM DIAGRAM A) Experimental Procedure—The alloys were prepared from NRC gas-free iron (99.9 pct Fe) and 99.99 pct Al. They were melted in alumina' crucubles under vacuum in an induction furnace. If the ingots were unsound or showed more than a 3 pct weight loss, they were rejected. The ingots were homogenized at 1100°C for 24 hr before hot-rolling at 700" to 900°C from 1 in. to 0.25 in. thick. It is interesting to note that alloys containing more than 28 at. pct Al were able to take an 80 pct reduction of area in the ordered FeAl region. The dilatometer specimens and specimens for chemical analysis were cut from these plates. A Leitz dilatometer was used to measure the coefficient of linear expansion as a function of temperature. The specimens were slowly cooled from 900" to 300°C where they were annealed for 10 hr before slowly cooling to room temperature. The expansion was recorded photographically as the alloys were heated and cooled at 1.5oC per min between 100" and 1000°C. The magnetic measurements determining the Curie points were performed on the dilatometer specimens in the dilatometer, by using direct current in the furnace windings both to heat the specimen at 1.5°C per min and to serve as the primary coil. The regular specimen holder was replaced by a thin alundum tube on which was wound, as a secondary, a closely spaced coil of fine copper wire. A reversal of current in the furnace windings produced, in the secondary, an emf which was proportional to the induction in the specimen, and which could be detected on a galvanometer. In this way, it was possible to determine the Curie points of alloys to within * 5°C. B) Results and Discussion—The coefficients of linear expansion, as obtained from the dilatometer curves, are plotted as a function of temperature and composition in Fig. 1. Since in many cases the heating and cooling curves were superimposed, it was decided to measure slopes of heating curves only. Definite high peaks, due to the transformations, were observed on each curve between 400" and 520°C, and, for alloys containing more than 23 at. pct Al, a second set of smaller peaks at temperatures above 660°C. The sharpness of the peaks indicates that ordering to Fe3Al is a first-order reaction. The compositions and the temperatures of these peaks are listed in Table I. When these temperatures are plotted as a function of the composition, the result is the constitution diagram presented in

Jan 1, 1960

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

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

Jan 1, 1942

By Antoni Kalukiewicz

From 1997 through 2000, a team of Polish experts headed by the author studied the prospects of mining newly discovered emerald deposits in Afghanistan. This article describes the scheme for mechanization of the mining operations, along with improvements made to the ventilation facilities and lighting. The required equipment was flown to Afghanistan and the Afghan miners were trained in machine operation and maintenance.

Jan 1, 2005

By Walter H. Bruckner, George B. Clark

Since the end of World War 11 interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Munroe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research on shaped explosive charges, the following have been established conceming cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the cone as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfonnance and more obtuse angles require thicker walls for the same base diameter. '. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, ten-sile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45" cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

By J. K. Stanley

Knowledge of the diffusivity of carbon in the low temperature form of iron (alpha iron existing below 910°C) is at the moment of considerable interest in the study of the decomposition of austenite and martensite, the elastic after-effect,123 the magnetic after-effect4 and the decarburization of steel below 910°C. Information on the solubility of carbon in iron, and to a lesser extent its diffusion, is also important in consideration of such phenomena as blue-brittleness, temper-brittleness, "magnetic" aging, quench-aging, strain-aging, and possibly the yield point. In order to obtain more information on these subjects more fundamental knowledge is necessary. It is the purpose of this work to present data on the diffusion and solubility of carbon in the alpha iron. The high temperature form of iron (gamma; face-centered cubic) existing above 910°C is capable of dissolving relatively large amounts of carbon, up to 1.7 pet at 1130°C, while the low temperature form (alpha, body-centered cubic) existing below 910° dissolves only a limited maximum amount of less than 0.02 pet carbon at 725°C, according to data obtained here. Since the solubility of carbon in the face-centered or gamma iron is large, relatively speaking, no great analytical difficulties have been encountered in the determination of the solubility lines5 or of the diffusion of carbon.0 The limited solubility of carbon in alpha iron offers difficulties because experimental procedures and analytical methods for low carbon contents below say 0.01 pet have to be more refined than techniques used for work with gamma iron. Because of the difficulties of applying conventional methods to the determination of the diffusion of carbon in alpha iron, virtually no work has been done on this subject. However, by proper refinement of the analytical method for small amounts of carbon, the determination of the diffusion coefficient can be made readily using modified procedures. The solubility of carbon in alpha iron has been determined over a temperature range by various investigators, but the agreement among them is poor. The present investigation establishes the limits quite accurately. Information of this kind is useful in establishing the correctness of equilibrium diagrams but, more significantly, such information on maximum solubilities, especially when extended to alloyed ferrites, should be extremely important in the study of aging and related phenomena. Literature The literature existing on the diffusion, in particular, and on the solubility of carbon in alpha iron is not extensive. The data which exist are not of a high order of accuracy, much of them being in the realm of conjecture. THE DIFFUSION OF CARBON IN ALPHA IRON Whiteley7 made the qualitative ob- servation, using metallographic techniques, that the rate of diffusion of carbon at the A1 (725°C) point was very rapid and that its diffusion was still rapid at 550°C. Snoek,4 studying the magnetic aftereffect in high purity iron, arrived at the conclusion that the after-effect could be explained by the presence of small amounts of carbon diffusing under the influence of magnetostrictive strain (lattice distortion due to magnetic interaction). In later work, Snoek8 made an estimate of the ratio of carbon diffusion in alpha to its diffusion in gamma iron, and concluded that for a temperature of 910°C the ratio of Da/D? was 2600. Polder,9 basing his calculations of D on relaxation phenomena in the elastic after-effect, estimated that Da is about 1/3 of D? at 910°C (1183°K) and is about 1/12 of Dy at 727°C (1000°K). Polder's equation for the diffusion of carbon in alpha iron was calculated to be 18000 D = 5.2 X 10-4 e-RT cm2 per sec Ham10 obtained data for the diffusion and solid solubility of carbon in alpha iron at two temperatures by using one technique similar to that employed in this study. He found a D of 8.0 X 10-7 cm2 per sec at 702°C and of 2.7 X 10-7 at 648°C. THE SOLUBILITY OF CARBON IN ALPHA IRON Although pearlite is absent in steels containing 0.06 pet,11 0.05 pet,12 or 0.045 pet C,13 it appears that the carbon in these steels cannot be in solution in ferrite. The solubility of carbon at the A1 (725°C) point was first determined by Scott14 on the basis of cooling curves, and was found to be between 0.03 and 0.04 pet C. Tamura15 by interpolating between the solubility of carbon in delta iron at 1400°C and in alpha at room temperature (assuming zero solubility) ar-

Jan 1, 1950

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

A satisfactory mathematical relationship between shear, elongation and change of orientation in the axial straining of a single crystalline rod or wire may be based on a simple model in which blocks, representing glide lamellae, glide over one another and rotate so as to maintain the original fixed position of the axis as the wire elongates.' Obviously such a model gives no information concerning strain-hardening or the atomic adjustments at the sliding surfaces and their influence on the internal structure of the blocks. Moreover such an operation could be conducted with rigid blocks only by using self-aligning grips or a flexible attachment which would permit the adjacent blocks to freely assume their changing orientations. There are many unsolved problems (see Andrade2) concerning the manner in which nature departs from the simple model in permitting the essentials of slip, rotation and elongation to occur along with strain-hardening and the appearance of glide lamellae of various dimensions and special characteristics, not fully appreciated at the present time. This paper describes part of an extensive investigation on the development and characteristics of glide ellipses in single crystalline alpha brass rods and is especially concerned with the observation of cross-slip in crystals oriented wholly within the range of slip on a single system according to the generalizations first presented by Taylor and Elam in 1923.³ Experimental Procedure Half-inch rods of alpha brass (nominally 70 pet Cu, 30 pet Zn)* were converted into single crystals by melting and gradual solidification in a graphite mold according to the Bridgman method.4 In order to remove any coring, the crystals were homogenized at 800°C for 16 hr and tested by etching with a 50 pet nitric acid solution. The back-reflection Laue technique as described by Greninger6 was used for determining the orientations of the crystals. Standard stereographic operations were employed to locate the specimen axis in a triangle of the Taylor and Elam3 projection so that the slip plane and direction could be predicted. The lineage structure reported by Buer-ger6 was present in the crystals used in this investigation. However, only crystals were used in which the internal differences in orientation did not exceed two degrees. Very little is known concerning the effect of the presence of a lineage structure on the detailed mechanism of plastic deformation.

Jan 1, 1949

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

A satisfactory mathematical relationship between shear, elongation and change of orientation in the axial straining of a single crystalline rod or wire may be based on a simple model in which blocks, representing glide lamellae, glide over one another and rotate so as to maintain the original fixed position of the axis as the wire elongates.' Obviously such a model gives no information concerning strain-hardening or the atomic adjustments at the sliding surfaces and their influence on the internal structure of the blocks. Moreover such an operation could be conducted with rigid blocks only by using self-aligning grips or a flexible attachment which would permit the adjacent blocks to freely assume their changing orientations. There are many unsolved problems (see Andrade2) concerning the manner in which nature departs from the simple model in permitting the essentials of slip, rotation and elongation to occur along with strain-hardening and the appearance of glide lamellae of various dimensions and special characteristics, not fully appreciated at the present time. This paper describes part of an extensive investigation on the development and characteristics of glide ellipses in single crystalline alpha brass rods and is especially concerned with the observation of cross-slip in crystals oriented wholly within the range of slip on a single system according to the generalizations first presented by Taylor and Elam in 1923.³ Experimental Procedure Half-inch rods of alpha brass (nominally 70 pet Cu, 30 pet Zn)* were converted into single crystals by melting and gradual solidification in a graphite mold according to the Bridgman method.4 In order to remove any coring, the crystals were homogenized at 800°C for 16 hr and tested by etching with a 50 pet nitric acid solution. The back-reflection Laue technique as described by Greninger6 was used for determining the orientations of the crystals. Standard stereographic operations were employed to locate the specimen axis in a triangle of the Taylor and Elam3 projection so that the slip plane and direction could be predicted. The lineage structure reported by Buer-ger6 was present in the crystals used in this investigation. However, only crystals were used in which the internal differences in orientation did not exceed two degrees. Very little is known concerning the effect of the presence of a lineage structure on the detailed mechanism of plastic deformation.

Jan 1, 1949

By A. A. Lavrinenko, N. I. Gluhova, L. M. Sarkisova, D. V. Makarov

"The investigated sulfide Cu-Ni ores are characterized by low PGE contents and emulgated impregnations of pentlandite and palladium minerals in the main ore-forming mineral pyrrhotite, which hinders their selective separation, requiring a collective flotation of sulfides to concentrate, and hydrometallurgical processing. As revealed by studies of floatability of Pt-Cu-Ni ore in a mixture of butyl xanthate and chelating phosphorus containing reagents, the most effective additive is Aerophine 3416 (a phosphinates mixture) manufactured by Cytec. Using collective flotation with a butyl xanthate – Aerophine 3416 composite in the ratio of 1:3 has afforded to enhance the Pt, Pd, and Ni recovery by 13.6 %, 9.2 %, and 9.4 %, respectively. The optimal ratios of Aerophine 3416 to butyl collector for the collective flotation are the following: 1:1 for Pt and Pd and 3:1 for Ni. The effect of these reagents on the electrode potential and surface hydrophobicity of pyrrhotite, pentlandite, and platinum black has been investigated. The extraction UV spectrophotometry experiments demonstrate that DIBDTPI exists on the pyrrhotite surface mainly in the form of disulfide in weak acid medium and in the form of compounds with Fe on the mineral surface in minute amounts. There appears some disulfide and few amount of (DIBDTPI)2Ni on the surface after interaction of DIBDTPI and pentlanditeINTRODUCTIONXanthates are widely used in flotation of copper-nickel ores containing platinum group metals (PGM) as sulfides collectors which can concentrate the most part of PGM connected with the sulfides. Though xanthates are hardly efficient for flotation of free PGM, the latter are floated more slowly compared to the sulfides of base metals. The reasons for poor floatation of free (mineral) forms of PGM are under-researched, however the key accepted reasons are: fine disseminations of free PGM, insufficient interaction with xanthate and negative influence of blue copperas and sulfur-containing ions which are sulfides oxidation products (Penberthy et al. 1999; Shackleton et al., 2007). That’s why an additional collector, normally dialkyldithiophosphates, is used during flotation of PGM-containing copper-nickel ores. A reagent DP-4 is used for recovery of PGM at Norilsk mining and metallurgical plant. The reagent represents a slightly-soluble organic calcium sulfonate which is given to flotation pulp in the form of water emulsion of 5% - solution in automotive diesel oil."

Jan 1, 2016