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By R. Schuhmann Jr., P. J. Ensio

As a first step in a study of the physical chemistry of copper-smelting slags, experimental measurements were made of the oxygen pressure of simple iron-silicate slags in equilibrium with solid iron. The experiments consisted in bubbling CO2-CO mixtures through the slags in iron crucibles and in finding the equilibrium ratios of CO2 to CO. From the data, activities and partial molal heats of solution FeO and SiO2 in the slags were calculated. THE ternary system FeO-Fe,O,-SiO, is the simplest system which can represent adequately the important chemical properties of the slags formed in matte smelting and converting. Accordingly, the experimental study of slags in this system was started as the first step in a general research program on the thermodynamics of copper smelting. A recent paper by one of the authors' outlines this general research program and shows in some detail how information on thermodynamic properties of iron-silicate slags, especially information on oxygen activities, is essential to a full understanding of the chemistry of copper smelting. The FeO-Fe,O,-SiO, system also is the basis of slags produced in other processes, such as acid steelmak-ing processes, and is important in relation to the behavior of silicious refractories. In addition, data on the physicochemical properties of iron-silicate slags should contribute to a general understanding of the nature of slags, since at present such data for all kinds of slags are relatively meager. The principal quantitative information already available on iron-silicate slags consists in Bowen and Schairer's constitution diagram for slags in equilibrium with metallic iron,' Darken and Gurry's complete and precise thermodynamic study of the Fe-0 system,",' and Darken's study of the phase equilibria in the Fe-Si-o system. From the results of this previous work, it was clear that a complete thermodynamic study of ternary iron-silicate melts was a major undertaking which would have to be broken down into parts, including the working out of the ternary equilibrium diagram as well as extensive activity measurements on slags. The experimental measurement of oxygen activity, using CO-CO, and other gas mixtures as yardsticks of oxygen activity, was the basis of Darken and Gurry's study of the Fe-0 system. From the experimental measurements of oxygen activities over a large range of temperatures and compositions, they were able to calculate the activities of other species such as Fe, FeO, Fe,O,, etc., and also the other important thermodynamic properties in the Fe-0 system. At the start of the present investigation, it appeared that the same approach would be fruitful for the study of iron-silicate melts. Also, the experimental measurement of oxygen activities seemed particularly attractive because oxygen activity itself is a quantitative measure of oxidizing or reducing power, which is an important variable in copper-smelting slags. The slag compositions in equilibrium with yFe appeared most suitable for the first investigation of this kind, for the following reasons: 1—Good constitution data2 were available. 2—An iron crucible could be used, thus affording a simple solution to the refractory problem without introducing contarnination. 3—With Fe activity fixed, at unity with respect to a standard state of solid Fe, measurements of 0 activity could be followed by simple calculations of activities of FeO and other Fe-0 complexes and of SiO,. 4—This starting point afforded several possibilities for cross-checking with previous work,

Jan 1, 1952

By J. L. Shafer, Christopher L. Caenepeel, Martha L. White

Often an in situ leach is the only practical economic method for copper recovery from small low grade oxide deposits. The decision to develop a copper property by an in situ blast and leach is strongly dependent on ore grade, tonnage, hydrology, and the copper extraction and acid consumption rates. The inherent leachability of the ore will in part determine the desired amount of fracturing of the ore deposit by the blast in order to obtain a copper extraction rate that is economical. For the last several years Occidental Research Corp. (ORC), has undertaken a modest effort to address the question of how to best identify and determine the information necessary to predict and control the operation of an in situ leach for the economic recovery of copper. Modelling of the Leaching Process During the past 10 years the activity in the mathematical modelling of the leaching of copper sulfides in copper dumps and heaps has increased dramatically. The modelling of copper oxide leaching has not received as much attention. The acid leaching of non-sulfide copper minerals while chemically less complex, compared to sulfides, does generate a vertical acid concentration gradient in the ore heap being leached due to the acid-base nature of the reaction. This is generally not observed in sulfide deposits that are biologically active, due to the buffering action of opposing reactions involving the generation of sulfuric acid from sulfide minerals and acid consuming host rock. Thus, the objective of ORC 's copper oxide modelling efforts is to determine the leaching parameters which will account for this vertical acid concentration gradient. Knowledge of this gradient will result in the correct choice of the feed acid concentration to the top of the ore dump or heap, such that the effluent will have the desired pH.

Jan 1, 1980

By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for, this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators 1.2.1 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By H. Reiss

The zone-melting process in which redistribution of solute in a solid bar is effected by the passage of a molten zone is considered mathematically. Simple approximate techniques are developed for computing the manner in which redistribution occurs as molten zones continue to pass. The introduction of the "zone-melting flux" provides valuable insight into the nature of the phenomenon, as well as a central mathematical theme in terms of which the process can be discussed. Curves are presented for typical and general cases. AN extremely efficient purification technique was described recently by Pfann.1 Known as zone refining, it consisted of the slow passage of a series of molten zones, produced by external heaters, through a long solid ingot of the substance to be purified. Equations were given for the maximum separation attainable, and a numerical computation method was described for obtaining the concentration in the ingot after a given number of zone passes. The present paper offers an interpretation of the physical nature of zone melting in terms of a transport process in which formal diffusive and convec-tive flows occur. This interpretation, in addition to providing insight into the physical nature of the process, also provides a basis for its mathematical treatment. From this basis, useful equations are developed for the solute concentration in the ingot as a function of the number of zone passes. These are applicable particularly where large numbers of passes are necessary and where numerical computational methods might be laborious. All considerations will deal with the limiting form of the process, described by Pfann,' in which: 1—Diffusion in the solid is considered negligible. 2—Mixing in the liquid is supposed, complete. 3—The distribution coefficient, k, measuring the ratio (at equilibrium) of solute concentration in the solid to that in the liquid is supposed, independent of composition. In general, this paper will be concerned with a bar of uniform (actually unit) cross section, ex- tending in the x-direction from x = 0 to x = L, where L may be infinite. Zone melting is a transport process, and as such must admit of interpretation in terms of a flux of transported quantity. However, the progress of operation is not measured in units of time but in terms of the number of completed zone passes. Consequently, the zone-melting flux will be a rate, per unit pass, rather than per unit time. The description of this flux and the examination of its properties is given below. Zone-Melting Flux Fig. 1 represents an intermediate stage of the nth pass. Concentration C is plotted against distance, x. The molten zone with its back at the point x and front at x + I moves in the direction indicated by the arrow. As it moves, it leaves behind the nth

Jan 1, 1955

By Enid C. Plante

To extend our knowledge of the flotation behavior of sulphide minerals, the response of the following minerals to ethyl xanthate as collector was studied by captive bubble and cylinder flotation tests: antimonite (Sb2S3), arsenopyrite (FeAsS), covellite (CuS), rnarcasite (FeS2), orpiment (As&.), pyrrhotite (FeS) and tetrahedrite (4CU2S, Sb2S3). Lollingite (FeAs2) was also exarnined to determine if its behavior could be correlated with that of pyrite or rnarcasite (FeS2. Experimental Method Mineral for Flolation and Contact Tests Mineral was prepared in the manner a1ready described1 and its behavior both freshly ground and "oxidized" was studied. Tests in which the mineral was allowed to oxidize for various periods showed that a uniform response to xanthate was reached in two days or less. Oxidation Products The soluble oxidation products from most of the above minerals were measured and their effect on the flotation of the mineral studied. The mineral samples were wet ground to minus-52 mesh and deslimed, and 20 g of this material placed in 200 ml of distilled water of a measured pH value, and CO2-free air bubbled through each suspension at a constant rate (about I bubble/sec) for 5 days. It has been shown1 that the size of the mineral is unimportant in the rate of formation , oxidation products and that probably the supply of oxygen to the mineral is the rate-determining step. At the end of 5 days the pH value of the 'supernatant liquid was measured again, the mineral filtered off and the soluble products determined. Methods for estimation of sulphur acids, ferrous and ferric iron and copper have already been described.l No satisfactory method was found for antimony. Arsenic was estimated as the arsenate.2 Flotation of "Unoxidized" Minerals with Ethyl Xanthate as Collector Fig I to 3, 4. 6, show the effect of alkali and cyanide as depressants for the minerals with 25 mg potassium ethyl xanthate per liter as collector at 35°C. Wark and Cox8 have shown that with ethyl xanthate as collector, galena, pyrite and chalcopyrite show a greater tolerance to cyanide and hydroxyl ions at room temperature than at 35°C Covellite (Fig I), marcasite (Fig 2) and pyrrhotite (Fig 3) behave similarly. The independence of the curves for pyrrhotite at 35°C with respect to cyanide

Jan 1, 1949

By R. W. Lai, I. Iwasaki

Some physical as well as chemical aspects of the methods of dispersion of various corn starches and their derivatives are investigated and their effects as depressants in anionic silica flotation of iron ores ascertained. The adsorption behavior of starches on hematite and quartz is strongly affected by their molecular sizes as inferred from viscosity measurements. The implication of this behavior on flotation and flocculation is discussed. Mechanical treatment of causticized starch solutions is shown to reduce the starch requirements in flotation appreciably. Starches and starch products have been used as depressants for iron oxides both in amine flotation of siliceous gangue and in soap flotation of activated silica from iron ores. Cooke and his associates1,2,3,4 extensively studied the effects of certain starches and their derivatives in the amine flotation of iron ores at near-neutral pH and found that although most starches were good flocculants for hematite and de- pressed that mineral more or less selectively1,3 they did not flocculate quartz suspensions. Further, that replacement of active groups in corn starch modified its behavior as a flocculant for hematite or quartz suspensions1 and as an iron oxide depressant. Schulz and cooke2 showed that many starches and their derivatives, except aminoethyl starch, were abstracted more effectively by Brazilian hematite than by quartz and that the adsorption of a starch product was strongly dependent on pH and on the presence of calcium ion. In soap flotation of calcium-activated quartz, certain starches and their products have been used to depress iron oxides.5'6 The behavior of these substances in flotation appears at times to be at variance with those previously reported and especially with results obtained in the Mines Experiment Station laboratories. This is attributed, at least in part, to differences in flotation procedure and flowsheets and in the method of preparing the depressant. Most of the investigators referred to above, solubilized the starch products by autoclaving at 120°C. Others have used acid,7 alkali8 or oxidizing agents.9 In view of the limited knowledge of the depressing action of starches and their derivatives in iron ore flotation, particularly in soap flotation of calcium-activated silica at high alkalinity, an extensive study

Jan 1, 1965

By Harry M. Mikami, A. Gene Sidler

Chemistry of the evolution of materials in contact with copper converter tuyeres is delineated by means of analyses of periodic punch rod samples taken during a converter cycle. Lining samples from known peripheral and end locations from three converters were investigated chemically and petrographically. One set of eight specimens representative of all lining parts was removed for study before completion of the campaign. Purely surface removal by slag action is minor. Slag filling of interconnecting cracks extending to the hot face results in a "stoping'' action which shapes the hot face contour and is a significant factor. Major wear mechanism is believed to be copper metal slabbbing caused by metal first penetrating joins and invading fractures or impregnating brick structure laterally from the joints. Importance of lining design and joint fit are emphasized. New laboratory tests are indicated. In the copper converter, molten matte, which is essentially a solution of iron and copper sulfides, is blown with air to produce blister copper. During the first stage of the process the FeS component is oxidized to SOz and FeO, the latter combining with a siliceous flux to form a predominantly ferrous silicate slag. Successive increments of matte and flux are charged, blown, and skimmed of slag until sufficient CuzS ("white metal") has accumulated. This white metal is then blown to copper metal in the final or blister-forming stage by the oxidation of sulfur to SOz and the reduction of combined copper to metal. The reactions of both stages are exothermic so provide the required heat. Temperature is controlled by cold scrap copper, flue dusts, smelter reverts, and so forth. Considerable vari- ation in practices occur depending on the type of converter, grades of the matte and flu, and other factors. Lathe and Hodnett's' survey of world converter practices gives much information on these variations and their effects on the refractories. Principles of converting chemistry are presented by Newton and wilson,' Ruddle,' and schuhmann. Most copper converting occurs within the temperature range 2100" to 2370°F although individual smelters report1 ranges from as low as 1700" to 2240°F to a high of 2200" to 2400°F. Temperature intervals reported from beginning to end of blow varied from 45" to 540°F. Average temperature range was 2030" to 2260°F and the average interval 250°F During the matte-blowing stage varying amounts of magnetite (FeO.Fe,O,) are formed in the slag as suspended crystals and also the liquid portion of the slag will contain, in addition to ferrous silicate, some Fe20s which adds to the potential magnetite formation if the temperature falls. This is a component of the so-called "dissolved magnetite" often referred to in the literature. Although the slag may contain minor amounts of CaO, A1209, MgO, and alkalies, the principal components are Fe0-Fez03-SiO,. The phase equilibria relationships of this system have been elucidated by Muan~ and Schuhmann, et a1.' These data and estimates of converting atmospheres by schuhmann4 are useful tools in studying slag behavior. It would appear that in many cases reported magnetite contents of slags are apparently higher than actually is present at operating temperature. This is probably because much of it is formed during slag solidification. The quaternary systems which have Mg-0,1,0,' and addition to iron oxides and silica are also of interest in considering the reactions of the slags with basic refractories. The formation of magnetite has an important interrelationship throughout the pyrometallurgy of copper (Mossman,' Gronningsater and Drummond," Ruddle,' Elwood and Henderson") but its presence in the converter particularly relates to operating efficiency and lining life in certain instances. Archi-

Jan 1, 1963

By Bruce R. Lipin

Chromite, the only ore of chromium, occurs almost exclusively in mafic-ultramafic rocks and their weathering products. However, not all kinds of mafic-ultramafic rocks are favorable hosts for possible low-grade chromite deposits. For instance, chromium-bearing basalts are not favorable because they commonly contain <0.3% Cr203, and chromite is almost always less than 50 mp in diameter, if it is present at all. Chromite-bearing ultramafic rocks in stratiform and alpine complexes tend to be either ore grade (>25% chromite) or very low grade (<2% chromite); intermediate rocks are scarce. In most complexes, large tonnages exist only in the <2% chromite rocks and the composition of the chromite in those rocks may be unsuitable for metallurgical use. Some nickel laterite districts contain more than lo8 tons of material with 2.0 to 5.5% Cr203, and hence, chromium could be a byproduct of nickel in some laterite districts. In addition, some chromiferous sand placers may contain tens to hundreds of millions of tons of material between 2 and 5% Cr203

Jan 1, 1983

By I. H. Warren, E. A. Devuyst

The selective dissolution of pyrolusite (MnO2) in presence of goethite (FeO•OH) in aqueous ammoniacal ammonium carbamate solution has been investigated: various reducing agents were studied, in particular sodium sulfite (Na2SO3,) and hydrazine hydrate (N2H4•H2O). Sodium sulfite was found to be an unsatisfactory reducing agent for both goethite and pyrolusite, for the leaching rate decreased steadily with time to an impractical level because of the limited solubility of the reactions products. Hydrazine hydrate was an effective reducing agent for pyrolusite even at low temperature, whereas goethite required much higher temperatures for any appreciable dissolution. A 1-hr leach at 35°C dissolved 90% of the pyrolusite but only 0.1% of the goethite. An activation energy of 17.0 Kcal per mole was found for the dissolution of pyrolusite with hydrazine. A reaction mechanism for the leaching of pyrolusite with hydrazine is proposed in which a reduction reaction on the surface of the mineral is the rate-determining step. The application of ammonium carbamate to the beneficiation of ilmenite is briefly described.

Jan 1, 1973

By H. R. Peiffer

Hardening of soft metals can be accomplished by dispersing finely divided hard particles in them. The dispersing of finely divided alumina in silver in the presence of oxygen yields a high strength material which is unusual in that its mechanical properties above the melting point of the continuous Ag-O alloy matrix are similar to other solids. The tensile strength is studied for two of these alloys, one of which contains 15 pct by weight alumina and the other 20 pct by weight alumina. The average fracture strengths above 960°C of these alloys were found to be 0.4 x106 dynes per sq cm and 3.8x106 dynes per sq cm respectively. The strengths appenred to be independent of temperature above 960° C. The creep behavior of the 20 pct alumina material was studied above 960°C. The initial creep rate, 6 , of this material can be represented by where s is the applied stress and E the activation energy for the process. This energy is of the order of 1.7 to 2.1 ev. HARDENING of soft metals by the addition of finely divided, hard particles has resulted in the production of materials with excellent creep resistance and with inhibited recrystallization.&apos; It has been demonstrated that such composites have useful strength up to temperatures very near the melting point of the soft metals, but one might expect that the strengthening by the dispersed particles ceases to be of importance above the melting point of the softer phase. This, however, is not so.2 In this paper the strengthening of a liquid Ag-O solution by the presence of dispersed alumina is discussed and experimental data concerning the mechanical properties of such a material at temperatures above 960°C presented. EXPERIMENTAL PROCEDURE Specimens were prepared using powder metallurgical techniques. Finely divided silver oxide was mixed in the appropriate proportions with "Linde B" alumina. For these experiments the specimens contained 15 or 20 wt pct alumina in pure silver.* These alloys were used in these experiments since they were the ones that could be handled readily enough to yield experimental data. Silver oxide was used in preference to silver because it is readily available in a very finely divided form and because the presence of excess oxygen in the silver is important to the properties2 of the material. The powders were mixed wet, using alcohol as the medium, in an ordinary food blender until a uniform mixture was obtained. They were then dried and heated to reduce the silver oxide to silver. Only a fraction of the finely divided silver remains unoxi-dized upon removal from the oven since the finest particles of silver oxidize immediately upon contact with air. The remaining fine silver served as a binder during pressing. The mixture was then pressed at 20 tons per sq in. into shoulder-grip (reduced section 1/4 in. by l/4 in. by 1 1/4 in.) and rectangular bar specimens (l/4 in. by 1/4 in. by 2 in.). The green specimens were heated very rapidly in a globar furnace to 1000°C, held at temperature untic they had reached theoretical density and then furnace cooled. The strength of the two compositions at temperatures above 960 °C was determined by pulling shoulder grip specimens inside a furnace mounted on a tensile machine. Specimens were gripped by means of wires wrapped around the shoulders of the specimen. Temperatures were measured by means of a chro-mel-alumel thermo-couple placed in the vicinity of the specimen. Control of temperature (within ±°15C) was accomplished by means of a Weston Recorder-Controller. Before loading, specimens were held at temperature for approximately 15 min in order to insure uniform specimen temperature. The low loads were measured by a special load cell designed by Baldwin Lima Hamilton. All testing was performed on a FGT testing machine of the same com-pany. Creep studies were performed in bending utilizing rectangular specimens of the 20 pct alumina alloy. Specimens supported at both ends by knife edges of inconel were placed in a globar furnace, heated quickly to temperature, and the deflection of the beam measured optically as a function of time. The weight and size of the specimen were predetermined and the maximum stress on the beam calculated from

Jan 1, 1962

By H. T. Green, R. M. Brick

True stress-strain data on alloys of pure iron with up to 2.4 pct Al were obtained in the temperature range +100° to —185°C. Alumi-num was found to reduce yield and flow stresses of iron at low temperatures but to have little or no effect on ductility. The effects of temperature and composition on strain hardening are discussed. SEVERAL independent studies of the behavior of high purity iron binary alloys at low temperatures are now in progress in attempts to evaluate systematically the variables affecting the low temperature brittleness of ferritic steels. This paper reports the results of one such investigation in which the tensile properties of aluminum and aluminum plus silicon ferrites were measured from 100" to —192°C. True stress-natural strain data have been obtained in order to evaluate as many as possible of the parameters which describe the behavior of the materials involved. In comparable studies at the National Physical Laboratory in England, iron and iron alloys of high purity have been produced&apos; and tested at subat-mospheric temperatures.&apos; True stress-natural strain curves were obtained there also. The purest iron contained 0.0025 pct C and 0.001 pct O and N. Even this, as normalized at 950°C following hot rolling, showed little ductility at -196°C. The grain size was ASTM No. 3, and the room-temperature yield strength was 17,800 psi (which seems too high for pure iron). Some of the NPL irons contained considerably more oxygen and demonstrated intergran-ular fracture at —196°C. The authors2 carefully differentiated between intergranular fractures associated with excessive oxygen content and transcrys-talline cleavage with little ductility encountered at —196°C in the purer material. The cleavage stress was half again as great as that associated with inter-granular fracture. Test Material, Preparation, and Procedures Of a number of Fe-A1 alloys produced, eight were considered to be sufficiently pure for testing. Partial chemical analyses (Table I), low observed yield points, and high ductilities indicate these alloys to be comparatively pure for vacuum-melted irons of sizable ingots, 5 Ib or more. To produce the binary Fe-A1 alloys, electrolytic iron was melted in air, cast into slabs, and rolled to strips 0.010 in. thick. These strips, joined into a continuous ribbon and wound into 2 1/2 in. diameter spools, were subjected for four weeks to a moving atmosphere of purified dry hydrogen in a stainless-steel tube at 1050" to 1150°C. Charges of these spools were melted in beryllia crucibles under good vacuums (1 micron), and aluminum (99.97 pct Al) was added to the melts. Compositions of these alloys are recorded in Table I. The ingots were hot forged and then cold rolled at least 65 pct to 3/8 in. rods which were vacuum annealed to the desired grain size, approximately ASTM No. 4, prior to machining into tensile test bars. All tensile specimens had gage sections 1 in. long, with a fillet of 1.5 in. radius to the shoulder. Gage diameters were 0.250 in, except for a few rods where additional cold work required use of a 0.200 in. gage section. After machining, 0.002 in. was removed from the gage diameter using 240, 400, and 600-grit metallo-graphic papers. The final polish with 600 grit left the fine scratches running in the longitudinal direction. By this means, surface metal strained during machining was removed. A few specimens heat treated after machining were similarly reduced 0.004 in. to remove any material affected chemically by the atmosphere during heat treatments, as is discussed in a later section. Tensile tests of the eight alloys at constant temperatures from +100° to —185°C were performed in apparatus which has been described." The essentials include a double-walled insulated metal vessel which contained the liquid heat-transfer medium surrounding the test specimen. A constant temperature was maintained by means of a pyrometer which regulated the pressure of dry air driving liquid air through a copper coil. Temperature variation was less than ±2°C during a specific test. For axial straining, two lengths of case-hardened chain, terminating in simple shackles, loaded the specimen through threaded grips. The lower grip bar passed through a hole in the bottom of the test vessel to which it was joined by a thin-walled

Jan 1, 1955

By E. Stamboliadis

Dithiophosphates are reaction products of phosphorous pentasulfide with various organic compounds such as phenols, alcohols, mercaptans, dioalcohols, amines, and nitrides. The products with alcohols are commercially known as "aerofloats" and these are investigated in this presentation. It appears that the formation of insoluble metal dithio phosphates is responsible for their collecting properties with minerals." In this aspect they are very similar to xanthates.3 The solubility of metal dithiophosphates depends on the number of carbon atoms in the organic chain of the corresponding alcohol. An empirical mathematical model is presented here. It allows one to predict the number of carbon atoms necessary to ensure that a certain metal dithiophosphate will form at a selected pH value of the water solution. The Nature of Dithiophosphates Dithiophosphoric acid is the product of the reaction of phosphorus pentasulfide with an alcohol, as shown in the following equation: [P2S3 + 4 ROH - 2 (RO)2 PS2H + H2S (1)] where R stands for a hydrocarbon chain. The acid so produced can be neutralized by a base to produce the corresponding salt as shown in the following: [(RO), PS2H + NH- (RO)2 PS, NH,. (2)] In this aspect dithiophosphates are similar to xanthates, the only difference being the substitution of the tetravalent carbon atom in the xanthate polar group by a pentavalent phosphorus atom in the dithiophosphate group. This difference implies at least two characteristics: (1) that there are two hydrocarbon chains associated with the polar group so that an increase in the number of carbons of the single chain is expected to have a pronounced effect on the flotation properties, and (2) that the bond between the sulfur and the central atom is stronger than in the xanthate group. This probably leads to a decrease in both the polarizability of the electronic cloud of the sulfur and the interaction with cations.3 However, what is lost in the dithiophosphates by having a weak polar group can be gained by an increase in the number of carbons as will be seen later. Taking into account the size of the atoms involved in a dithiophosphate molecule, as listed in Table 1, It is possible to draw an approximate diagram of its structure as shown in [Fig. 1]. It is assumed here that the length of the single hydrocarbon chain is equal to that of the corresponding alcohol. Preparation and Purification Acid dithiophosphates can be prepared, as previously mentioned, in accordance with Eq. 1. The rate of this reaction is too slow at room temperature and can be improved by increasing the temperature to about 60° or 80°C7 or by evacuating the system. In our investigation evacuation was performed by a water aspiration pump. The dithiophosphoric acid so produced is liquid and dissolves in the alcohol. At the end of the reaction the product is filtered from the remaining P2S3; and dissolved in petroleum ether. By blowing anhydrous ammonia gas into the ether phase the ammonium salt forms as a white precipitate and can be sepa-

Jan 1, 1977

By M. J. Mullikin, J. B. Conway

Several different equation forms were studied to determine the extent to which each particular equation type yielded an accurate representation of a given set of first-stage creep data. Specially developed least-squares computer programs were employed to obtain unique solutions for the creep-equation constants. In studies of creep data for lead at 14.5"C, nickel at 70OCC, and arc-cast tungsten at 2400°C consistently good representations were afforded by a third-degvee polynomial in t113. Other effective correlations were obtained with the Andrade, Cottrell-Aytekin, and de Lacombe equations along with a third-degree polynomial in t112. A newly proposed creep equation involving a hyperbolic-sine term in t1&apos;3 was also found to yield very satisfactory results. This appears to be the first use of such a functional relationship in the analysis of transient creep behavior. In general, the deformation behavior of a material subjected to a tensile load is described in a strain-time plot. Experiments have shown that, following the instantaneous elongation which results on loading, the instantaneous slope (i.e., creep rate) of the strain-time curve decreases gradually with time and approaches what appears to be a constant value. Equations, therefore, which are proposed to provide an analytical representation of such first-stage or transient creep behavior must be consistent with these observations. In other words, at time zero, these equations must yield a finite deformation value corresponding to the elongation on loading. Furthermore, the first derivative of these equations must exhibit a fairly high although finite value at time zero, and then values which decrease with time. It is also preferable, in general, that the derivative eventually assume a constant value at high time values. Although many studies of first-stage creep behavior have been made and numerous equation forms have been proposed for expressing this type of deformation behavior, it is still not possible to state with any assurance which functional relationship will be adequate for a given set of measurements. Parabolic relationships have been employed most extensively although logarithmic expressions have been shown to be applicable in some instances. Combined forms1 have been studied in considerable detail and have on occasion been found to be very effective. One such expression is that of iXndradea and involves a modified parabolic expression: where 1 is the instantaneous length, lo is the length immediately following load application, t is the time, and p and k are constants. Another combined form has been proposed by weaver3 as follows: where E is the instantaneous strain, is is the linear creep rate, t is the time, and a and b are constants.

Jan 1, 1967

By H. R. Gardner

The heat treatmmt of plutonium was studied using the Jominy end-quenching technique commonly used for determining the hardenability of steel. Plutonium specimens were end-guenched from temperatures in each of the ß, y, d, d&apos;) and E phases. One series of specimens with a low-iron content, 165 pprn Fe, and another gvoup with a high-iron content, 678 pprn Fe, were used in order to study the effect of a Pu-Pu,Fe eutectic network on the hardness and micro-structure. Hardness traverses indicated no significant variations in hardness with either cooling rate or quench temperature. Metallographic studies indicated major effects on microstructure. Grain size was found to vary markedly with quenching temperature and cooling rate. It was determined that the Pu-PueFe eutectic network could be modified extensively by heat treatment, including spheroi -dization in the y phase and 6 phase below 413°C. An unidentified spheroidal inclusion was observed to go into solution in the delta and higher temperature phases. 1 HE element plutonium is unique among metals in that it has six allotropic forms in the solid state.&apos; These have been designated&apos; as the a, ß, y, d, d&apos;, and phases. The respective phase transformations occur at approximate temperatures of 122", 210°, 319°, 450°, and 480°C with a melting point at 640°C. With this number of phase transformations it becomes pertinent to consider the effect of heat treatment and cooling rate in the various phases on the microstructure and hardness of plutonium. To determine; the effect of a wide range of cooling rates, the Jominy end-quenching technique was applied to cylindrical plutonium specimens. In addition, since the presence of iron in amounts greater than 500 pprn is common in plutonium and results in a network of the Pu-Pu6Fe eutectic, it was decided to study heat treatment effects on two bomb reduced plutonium buttons with different iron contents. A low iron button containing 165 ppm Fe and a high iron button containing 678 ppm Fe were selected for this comparison. EXPERIMENTAL PROCEDURE Experimental Material. The cylindrical bars for Jominy quenching were cast from button stock in vacuo in MgO coated graphite molds. Metal pouring temperature was approximately 950°C and the molds were preheated to 300°C. The castings were machined to 0.5 in. diam. by 2.5 in. long cylinders. Chemical analysis and density data for the two groups of Jominy specimens containing different iron contents are presented in Table I. Except for iron, heats 19-12-1 and 20-2-1 are comparable within the limits of analytical accuracy. Representative specimens from the low-iron and high-iron bars were taken for metallographic examination. The low iron specimen was found to have extensive microcracking, Fig. 1. In addition, numerous unidentified spheroidal inclusions were present, Fig. 17. The average grain size of the low-iron plutonium is 0.068 mm, Fig. 4. In the high-iron plutonium, a Pu-Pu6Fe eutectic network is prominent, Fig. 7. The average size of the network is 0.100 mm. Unidentified spheroidal inclusions were also common in the high-iron plutonium. The average grain size of the high-iron plutonium is 0.036 mm. Experimental Technique. A Jominy end-quenching fixture was fabricated for glove box use. A 2.5 in. water height was used with an orifice of 0.250 in. ID. The orifice to specimen distance was maintained at 0.5 in. Annealing temperatures of 160°, 265°, 400°, 465°, and 535°c were chosen for the study of the effect of quenching from ß, y, d, d&apos;, and e phases on microstructure and hardness. During quenching, cooling curves were obtained from the Jominy specimens at distances from the quenched end of 1/16, 1/8, 3/8, 3/4, 1-1/4, and 2 in. Cooling rate calculations were made from the cooling curves for temperature intervals of 100° to 110° 160" to 170°, 330" to 340°, 420° to 430°, and 490° to 500°c. These temperature intervals were chosen

Jan 1, 1962

By P. E. Busby, C. Wells, M. E. Warga

Fundamental data on the rate of diffusion of boron in austenite and solubility of boron in the a and y phases of iron and steel have been obtained from deboronizing experiments and provide partial explanations for some of the phenomena observed in boron steels. The rate of diffusion of boron is about the same as carbon in austenite. The solubility of boron in austenite at normal heat-treating temperatures is less than 0.001 pct. A partial tentative Fe-B phase diagram in the important low boron concentration ranges and an equation representing the diffusion of boron in austenite are presented. A LTHOUGH a search of the literature revealed ALTHOUGHthat boron diffusion had not been studied quantitatively and systematically prior to 1948, a few qualitative observations which were made by following the diffusion of boron into iron packed in ferro-boron1-3 suggest that boron obeys normal diffusion laws and that the rate of diffusion increases with increasing temperature. The claim of Cornelius and Bollenrath1 that boron does not appear to influence the rate of carbon diffusion has recently been substantiated by Wells, Batz, and Mehl.4 Calculations based on data from the paper by Campbell and Fayv indicated that the diffusion coefficient (D) for boron in iron at 900°C is approximately 3x10 sq cm per sec; a value of 2x10-7 sq cm per sec at 1038°C has been reported by Digges et al in connection with decarburizing experiments on a commercial boron steel containing 0.43 pct C. During the period 1948 to 1950 several diffusivity constant (D) values for the diffusion of boron in the y phase of iron and steel and a number of solubility values for boron in both a and y phases were reported. It was concluded tentatively as a result of Metals Research Laboratory studies that D values for boron in y and a phases are about the same as for carbon in the comparable phasesa and that carbon up to 0.4 pct did not affect the rate of diffusion of boron in y iron above 1000°C within the limits of experimental error. Whether saturation of the y or a phases with carbon would significantly affect rates of diffusion of boron through them was then and still remains in doubt. The best estimate of Q (activation energy) was reported to be about 25,000 cal, somewhat lower than that for carbon in y iron. The solubility of boron in y iron at 1000°C was thought to be higher than 0.004 pct B but not as high as a more recent analysis of available data shows it to be. The solubility of boron in a iron at 700°C was reported to be 0.0004 pct B, but it would not have surprised the authors if the true solubility value is actually lower than this. Breaks in diffusion curves which were not understood when first obtained prior to 1950 have now been recognized as indicating solubility limits, and these are included in the present paper. Experimental Procedure Two methods were employed in an effort to determine diffusion coefficients (D) for boron in austenite. Early experiments involved the use of welded couples prepared in accordance with the procedure of Wells and Mehl,&apos; but when the results of these experiments proved to be unsatisfactory for calculating D values, studies were continued by means of deboronizing experiments. In both cases, boron analyses following the diffusion anneal were carried out spectrographically and all D values were computed using the Grube solution of Fick&apos;s law. The precision of the spectrographic method used proved to be about equal to that reported by Corliss and Scribner" —average deviation from the mean about 5 pct of the amount present when the boron content is 0.003 pct. Concentration-penetration curves obtained from spectrographic analyses of welded couples generally indicated that practically no boron was transported across the weld interface during the diffusion anneal. Furthermore the concentration-penetration

Jan 1, 1954

By Appendix by A. S. Goldoni, R. E. Tate, E. M. Cramer

The diffision coefficient for self-diffision of plutonium in the temperature range 350" to 440°C has been measured by using puZ3 as the tracer isotope. Autoradiopaphic techniques were used to inzlestigate the possibility of grain boundary diffusion, hut only evidence for volume diffusion was found. The least-squares fit of the data gives the .following equation for the diffision coefficient: The computer least-squares technique for fitting the nonlinear equations is outlined. DETERMINATION of the self-diffusion coefficient of the fcc 6 phase of plutonium is in principle a straightforward experimental task. However, the chemical reactivity, the intense @ activity, and the toxicity of plutonium put limitations on the experimental techniques. The technique selected included roll bonding for preparation of the diffusion couples and pulse-height analysis of the @-particle activity to determine the distribution of the PU tracer in the diffusion couples. EXPERIMENTAL PROCEDURE Couple Preparation. Cylinders about 0.5 in. in diam were cast from two special stocks of plutonium, one of which had been enriched in puZ3&apos;, as shown in the isotopic analyses listed in Table I. For each roll-bonded composite sheet, a cylinder 0.437 in. in diam and 0.190 in. thick was turned from each kind of plutonium on a lathe in a 98 pct He atmosphere. The two freshly machined cylinders were positioned face to face in a tube of commercially pure aluminum which had been sealed at one end by welding and the assembly was evacuated on a vacuum manifold overnight. The elapsed time between machining the faces of the plutonium cylinders and evacuating the loaded tube was about 15 min. After overnight evacuation of the assembly the indicated vacuum was 1 X 10"5 torr or better. The aluminum tube was then warmed and pinched off with a cold-welding tool. The pinched-off weld was also fusion-welded as an additional precaution against leakage of air into the evacuated assembly. The assembly was immediately heated for 30 min in a 250°C furnace and reduced in thickness by being passed through a rolling mill with rolls heated to 200°C. The rolling schedule (four passes of 100 mils each with a 10-min reheat after two passes) reduced the thickness of the assembly to 100 mils. The rolled assembly was allowed to cool normally in air. The rolled assembly was sheared at the edges and the aluminum peeled from the composite plutonium sheet. The elliptical sheet was about 0.060 in. thick and usually three 0.383-in.-diam disks could be punched from its central portion. The sheet was heated on a hot plate to the ductile low 0 range (140°C as measured by temperature-indicating pellets) before each disk was quickly punched. The quality of the bond in the disks was evaluated by metallographic examination of the scrap sheet adjoining the hole left by the punch. Only well-bonded specimens without oxide in the interface (as indicated by metallography) were considered satisfactory for further use. More than half of the specimens so examined contained sufficient oxide in the interface to be rejected. Diffusion Anneal. Each disk to be diffusion-annealed was wrapped in 1-mil-thick tantalum foil and sealed within a Pyrex capsule evacuated to 1 x 10~5 torr or better. This capsule was then sealed within another Pyrex capsule at a similar pressure. The diffusion anneals were carried out at temperatures between 350" and 440°C in Marshall furnaces adjusted to have a temperature gradient of not more than *1/2"C over a 5-in. length. This gradient was then further smoothed by using a nickel tube as a liner in the furnace. The liner was divided into three longitudinal cavities by a septum of nickel sheet to which two calibrated Chromel-Alumel thermocouples were attached. One thermocouple was used for controlling the furnace temperature by means of a Brown Pyrovane controller equipped with a Capaciline anticipation circuit; the second thermocouple was monitored twice daily with a Leeds and Northrup K-2 precision potentiometer.

Jan 1, 1964

By J. H. Brophy, S. J. Michalik

A constitution diagram for the system Mo-Ir has been determined. The maximum solubility of iridium in molybdenum is 16 at. pct at 2110ºC and decreases to less than 5 at. pct at 1500°C. The solubility of molybdenum in iridium is 22 at. pct. Three intermediate phases appear in the system: 8 MoJr, having the p-tungsten structure; a phase, a cornplex tetragonal structure; and the hcp ? phase. Metallography, melting point determinations, X-ray diffraction and fluorescence, and electron micro-probe unalyses were employed in establishing the diagram. PREVIOUS to the present investigation, the intermediate phases in the Mo-Ir system were identified, but no detailed account of the phase diagram has been reported in the literature. Raub1 investigated alloys of Mo-Ir over an extensive range of composition between the temperatures of 800º and 1600°C. The in-termetallic compound MosIr was found to exist with nearly pure molybdenum, as the solubility of iridium in molybdenum was not detectable parametrically in this temperature range. MO3Ir was found to be iso-morphic with a ß-tungsten type structure, having a parameter of 4.959Å. An intermediate hcp phase, designated as the ? phase, ranged in composition from 52 to 78.5 at. pct at 800ºC, and from 41 to 78.5 at. pct Ir at 1200°C. Parameters noted for the ? phase were as follows: at 42.7 at. pct Ir, a = 2.771i0, c = 4.4366, c/a = 1.601; at 78.5 at. pct Ir, a = 2.736A, c = 4.378A, c/a = 1.600. Molybdenum was found to be soluble in iridium up to 16.5 at. pct Mo (83.5 at. pct Irj, with the parameter of iridium increasing to 3.845A at the solubility limit. Knapton,2 who investigated alloys between 15 and 85 at. pct Ir, essentially agreed with Raub&apos;s data, but, in addition, found a a phase in as-melted alloys near 25 at. pcto Ir. The oaphase lattice parameters were a = 9.64Å, c = 4.96Å, c/a = 0.515. The a phase was replaced by the 8 -tungsten phase on annealing at 1600°C. Knapton concluded that the a was stable only at elevated temperatures, and placed the composition of the a phase at approximately 30 at. pct Ir. The intermetallic compound Mo3Ir, with a lattice parameter of 4.965A, was included among the 8-tungsten structures reported by ~eller.&apos; Matthias and Corenzwit,4 and Bucke15 studied the superconducting nature of MosIr, and reported a superconducting transition temperature of 8.$K. The present investigation describes the phase relationships in the Mo-Ir alloy system determined by melting point measurements, X-ray diffraction and fluorescence, and metallography. EXPERIMENTAL PROCEDURES Alloys for the determination of the phase diagram were prepared from powders. Commercial 99.9 pct Mo from Fansteel Metallurgical Corp. and 99.9 pct Ir powder from J. Bishop and Co. Platinum Works were used. The powders were weighed to nominal compositions, mixed, and then pressed, without binder, into compacts weighing 4 to 6 g. These were presintered in uacuo between 1200&apos; and 1400°C for 1 hr, to reduce the degree of spattering during subsequent arc-melting. The compacts were arc-melted in a nonconsumable tungsten electrode furnace six times on alternate sides on a water-cooled copper hearth in an atmosphere of zirconium-getter ed argon at 500 mm of mercury pressure. In almost all cases, this procedure yielded buttons of satisfactory homogeneity. The composition of all melted buttons were confirmed by X-ray fluorescent analysis using the experimentally determined ratio of the iridium La1 line intensity to that of the molybdenum Ka1 line as a function of composition. In this determination four alloys analyzed by wet chemical methods were used as standards. An uncertainty range of ±1 at. pct has been attributed to all indicated compositions. All heat treatments and solidus measurements were carried out in tantalum resistance heating elements in vacuum conditions of 10-4 to 10-5 mm of mercury. A detailed account of this procedure has been reported by Schwarzkopf and Brophy.8 In the heat treatment and solidus measurements of iridium-rich alloys (50 at. pct Ir or greater), a tungsten lining was inserted into the tantalum resistance heating element because of a eutectic reaction which occurs between iridium and tantalum at 1948ºc.7 Heat treatments and solidus measurements carried out at compositions less than 40 at. pct Ir both with and without tungsten linings within the resistance

Jan 1, 1963

By W. A. Wood, H. L. Wain, R. I. Garrod

The mechanical behavior of recrystallized chromil~m of high purity has been studied, principally in torsion and to a lesser extent in tension, at temperatures between —196oand 350oC. Depending upon the conditions of test, the material may show brittle or ductile behavior or an intermediate or subduc-tile state having some of the characteristics of each. This latter state existed at temperatures between approximately ±50°C and was characterized by a) extensive creep at stresses well below the normal fracture stress, b) nonelastic loading/unloading effects during creep, c) strain softening under cyclic loading, and d) final failure of a brittle type. Suggestions are made on the dislocation processes and interactions which give rise to subductile behavior The ductile-brittle transition in bee metals has been studied mainly by tension and bend tests. These methods, however, favor crack propagation which may follow too closely on initiation for detailed study of the transition itself. For work of this nature, therefore, other modes of deformation less favorable to crack propagation may be preferable. This paper describes a study of the ductile-brittle transition in chromium which is based mainly on torsional testing although a few subsidiary experiments were made in tension. It appears to reveal at the transition an intermediate state that cannot properly be described as either brittle or ductile. Torsional tests on chromium have been made by other workers1 but not, as here, primarily for study of this intermediate state. EXPERIMENTAL The chromium, in the form of swaged rod, was prepared by techniques already described.&apos; The particular material used was one in which the main impurities were 0.03 wt pet 0 and 0.006 wt pet N and one in which transition from ductile to brittle states in torsion conveniently fell at about room temperature. For torsion, test specimens were from 5/16-in.-diam rod to provide test portions 1-1/4 in. long by 7/32 in. diam, a twist of 1 deg thereby corresponding throughout this paper to 0.0015 surface shear. The specimens before test were annealed for 2 hr at 1200°C in vacuo, which left them with a re-crystallized grain size of about 0.01 mm, and then electropolished. They were tested under dead-weight loading in an apparatus in which they could be surrounded by a furnace or cooling chamber, tests in practice being made at various temperatures between -196" and +350°C. For tension tests, cylindrical specimens were prepared in a similar manner and tested at room temperature under dead-weight loading. RESULTS (TORSION) Subductile State. The state described above as intermediate between brittle and ductile may be perhaps best defined by reference to torque/twist curves at various temperatures. These are grouped in Fig. 1. Below about -50°C the material was brittle, in the sense that it exhibited little plastic deformation under stress and fractured by cleavage along planes of maximum resolved tension, which in torsion produces the well-known helical type of fracture. The deformation is typified by the curves for -196" and -150°C in Fig. 1; it shows a slight but progressive deviation from linearity above a certain torque, here about 50 lb-in., until fracture occurs at about 95 lb-in. A feature to which it is desired specially to call attention is that under none of the loads did the specimens show significant creep.

Jan 1, 1964

By Henry Hebley

IN preparing this paper it has been the aim of the writer to keep the problems of both producers and consumers in mind. Until now, no attempt has been made to familiarize each group with the other&apos;s practice and limitations. This paper is an effort to acquaint the readers with some of the factors pertaining to the problem and cost of mining and preparing steam coal, and also to the economics of producing steam with such coal. In recent years all lines of endeavor have turned to intensive mechani-zation in order to lower the unit cost of production. The average fuel consumption in steam electric generating stations has dropped in 20 years from 4.0 lb. to 1.4.1b. per kilowatt-hour; while the modern power station can generate 1 kw-hr. on a fraction under 1 lb., or 13,000 B.t.u. coal. Also, the amount produced per man has in that same period risen from 3.8 to 8.2 tons, owing to the use of modernized equipment below ground for coal cutting, drilling, shooting, loading, hauling and hoisting. Unfortunately, the rapid speed of 5 tons per minute of operation at which the coal is loaded mechanically precludes any appreciable removal of impurities at the coal face, so that the raw coal is hoisted containing a markedly higher percentage of impurities than the hand-loaded coal, which was subjected to the scrutiny of the miner during loading. Also, during the past 20 years, certain seams of coal lying close to the surface have been made economically available by the improved design of electrically operated shovels and draglines for the removal of overbur-den running as high as 56 ft. This strip coal frequently contains so much ash in the raw state (Table 1) that it would have no sales value. There-fore, coal preparation must be adopted to beneficiate the raw product. Some seams in the United States have a decreasing ash content with decreasing size, owing, in all probability, to the fact that the coal is friable while the impurities are hard, causing a concentration of the low-ash material in the fine sizes. Illinois No. 6 coal being rather hard, naturally the reverse is true.

Jan 1, 1937

By F. W. Warnaars

The Los Bronces copper deposit is located on the west side of the Andes Mountains in central Chile about 54 km (34 miles) northeast of Santiago. The deposit consists of a hydrothermal breccia complex that was emplaced in the western part of an earlier porphyry copper mineral system. This system exhibits propylitic, sericitic, silicic to potassic hydrothermal alteration with disseminated and stockwork copper-molybdenum sulfide mineralization over an area of about 12 km2 (5 sq. miles). The Rio Blanco Mine, about 800 m (0.5 miles) east of Los Bronces, is an underground block caving mine located in the central part of this system. The mineralization at Rio Blanco is characterized by one of the highest primary copper grades known for porphyry copper systems. Present mining at Los Bronces is from an open pit located in the northern part of a hydrothermal complex that is composed of at least seven different copper-bearing tourmaline breccia pipes. Together these pipe form one large contiguous body about 2 km (1.2 miles) long and 0.7 km (0.4 miles) wide at the surface. This body crops out at elevations of between 3.5 and 4.1 km (2 and 2.5 miles) above sea level. Each breccia pipe has a characteristic shape, matrix, type and degree of mineralization and alteration. Quartz, tourmaline, specularite, anhydrite, pyrite, chalcopyrite, sericite, chlorite, and rock flour are present in significant quantities in most breccia matrices. The clasts consist mainly of quartz monzonite, andesite, and minor amounts of quartz latite porphyry. The seven different breccia pipes are identified, from oldest to youngest, as Ghost, Central, Western, Infiernillo, Fine Gray, Anhydrite, and Donoso. The breccias coalesce, interfinger, or display gradational contacts. In places they form sharp contacts with each other and with the surrounding intrusive or volcanic host rocks. Early breccias are disrupted or cut by subsequent breccia events. Explosive emplacement was followed by collapse after the release of hydrothermal pressures. The Los Bronces breccia complex has sharp contacts with the surrounding intrusive stock and andesites. These contacts dip inward on the north, west, and south margins. The eastern contact is nearly vertical and/or dips slightly outward and suggests a westward tilting of the body of about 15° after emplacement. The breccia complex is not fully explored at depth, but is known to extend at least below the 3 km (2 mile) elevation in its central eastern part, about 1 km (0.6 miles) below the highest breccia outcrop. Primary copper sulfide minerals are most abundant in the Donoso and Infiernillo breccias where the matrix consists mostly of tourmaline, quartz, sulfides, specularite, and/or chlorite with minor amounts of rock flour, sericite, and clay. The volume of the matrix material is mostly smaller than in the other breccias. Secondary enrichment enhanced the primary copper grade in the southern two-thirds of the Los Bronces breccia complex and in much of the surrounding porphyry system. Primary grades of 0.3% to 0.5% copper have been enriched to approximately 0.9%. This enrichment may extend from surface outcrops to a depth of more than 500 m (1, 640 ft) in more permeable parts of the breccia complex. A leached and oxidized capping of variable thickness covers a large part of the enriched layer and exceeds 300 m (984 ft) at one location. The shape and depth of the enrichment blanket and the capping suggest that the enrichment process is still active.

Jan 1, 1983