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By V. F. Hollister

Although it is apparent that porphyry copper deposits may have formed in the Andean orogen from Permian time onward, commercial deposits thus far developed appear to have Cenozoic ages only. Following Chilean usage, the porphyry deposits are divided into either (1) a stockwork or (2) a tourmaline breccia model. As indicated by evidence cited in the paper, stockwork-type deposits tend to be related to major strike-slip structures which may be either transcurrent or transverse faults related to plate movements, while the tourmaline breccia type may more frequently form independently of regional faults. Stockwork types may be conjugate fractures that intersect and ramify as a network of veins and veinlets, cutting altered rock, and genetically related to a major regional fault, or in other cases they may reflect the intersection of two large fault structures. Circular fracture patterns may more rarely occur in stockwork deposits in response to a specific intrusion. Tourmaline breccia types are characterized by circular and radial fractures genetically connected in some way with touramline breccia pipe development or an intrusive piercement that preceded it. Each structural model contains mineralized intrusions which have a close time-space relationship to ore, and in each model mineral paragenesis is similar, regardless of age or location in the plate. Also, each model contains the same type of alteration halos (phyllic, argillic, propylitic) as are developed in intrusive centers in porphyry copper deposits found in North America. The potassic zone is exposed best in the older deposits. Examples of each type of deposit are illustrated, demonstrating the feature evolved.

Jan 1, 1975

Discussion of the paper of J. V. EMMONS, presented at the Pittsburgh meeting, October, 1914. and printed in Bulletin No. 93, September, 1914, pp. 2233 to 2248. ALBERT SAUVEUR, Cambridge, Mass.-Mr. Emmons is to be congratulated for having placed before us in so forcible and satisfactory a manner a question of much importance-that of the surface decarbonization of steel. Of course, both manufacturers and consumers have known for many years that during the heat treatment of high-carbon steel, surface deca.rbonization is always likely to occur to a greater or less degree, but the subject does not seem to have been investigated with the method and thoroughness it deserves. I am in substantial agreement with Mr. Emmons's conclusions, and I have but little to add to what he has so well said. His statement that carbon dioxide is just as effective an oxidizing agent as pure oxygen is likely to cause surprise and some will wonder whether his investigation has been carried far enough to warrant so unexpected a conclusion. The reaction C + 0 = CO, expressing the oxidation of carbon by pure oxygen, is decidedly exothermic, whereas the reaction C + C02 = 2C0, expressing the oxidation of carbon by carbon dioxide, is endothermic. Decarburization by pure oxygen, therefore, should take place much more readily than by carbon dioxide. One cannot help regretting that the author does not mention' the best way of preventing in a practical manner surface decarbonization while treating tool steel and other high-carbon steels.

Jan 4, 1915

By S. Norton

GEORGE C. FOOTS, Port Henry, N. Y. (written discussion).-The paper by Mr. Norton and Mr. LeFevre will bear the most careful consideration by all interested in the iron business, particularly in the East. There is much information contained therein which should be emphasized. The idea of handling iron-bearing rock in quantities comparable to the porphyry coppers does seem at first blush to be beyond the pale of commercial possibility. Yet, today in the Adirondack region 25 per cent.

Jan 4, 1917

By William Fink

THE investigation of aluminum alloy systems prior to 1923 was severely handicapped by the low purity of the best aluminum available. However, by that time, the electrolytic purification of aluminum had been developed by the Aluminum Company of America,(1)? and in May, 1923, there was initiated, under the direction of E. H. Dix, Jr.,(2) a program for the investigation of the aluminum-alloy systems using the purest electrolytically refined aluminum. Up to the present time 15 papers (a) have been published, most of which are on the binary aluminum systems. Work is now in progress on the ternary systems, and it seems probable that most of the future work will be on ternary systems. Therefore this survey of the binary aluminum systems investigated up to the present time (the sixteenth paper of the series) concludes the first phase of this program. Certain qualitative relations between corresponding portions of the various binary diagrams as well as between different parts of the same diagram were noted some time ago by R. S. Archer.(4) In the present . paper these relations and others are considered quantitatively by the application of well-known thermodynamic equations or by newly discovered empirical relations No attempt will be made here to present the history of the develop-ment of the thermodynamic equations defining equilibrium or their application to metallic systems, although a list of references is given at the end of this paper for those who are interested in this phase of the

Jan 1, 1934

THE Institute of Metals Division of the American Institute of Mining and Metallurgical Engineers appointed a Research Committee in 1925 to de-termine what could be done by the Division to promote research work in the United States on non-ferrous metals. It was recognized that a considerable volume of use-ful research work in this field was being carried on by individual industrial companies as well as by the uni-versities and other research institutions, such as the Bureau of Standards. One need only refer to the recent research literature on non-ferrous metals in the TRANS-ACTIONS of the A.I.M.E., and elsewhere, to be con-vinced of healthful research activity in this field. The appointment of the Committee, however, voiced the impression that what was being done was, however excellent, inadequate for the needs of the industry. It was felt that the Division could usefully devote some of its time and effort in stimulating activity in this field. The deliberations of the Research Committee have not failed to develop wide differences of opinion even on the simple questions: (1) whether the Division can aid in any practical manner in this cause and (2) what the features of such aid might be. However, it was clear that there was only one type of research activity with which it could be very usefully concerned, viz., that on subjects of fundamental interest and general application. It was obvious that research work having special objects and more immediate commercial appli-cation should best be left to the industry itself.

Jan 1, 1927

By Roy P. Hudson

A micropyrometer known as the De Graaf apparatus has several advantages over the gas-furnace method for determining ash fusibility. When the De Graaf apparatus is operated by a modified method of procedure, the results closely check those of the gas-furnace method. This is indicated by tests on 27 samples of coal ash, with an extreme variation in fusibility values of 654" F. However, most of the ashes fused at temperatures between 2300º and 2500º. This, presumably, is the temperature interval within which the micropyrometer gives the best results. Additional comparisons are desirable. DISCUSSION (Thomas G. Fear presiding) A. C. FIELDNER,† Washington, D. C. (written discussion‡).-—The Pittsburgh Experiment Station of the Bureau of Mines has made two investigations1 of the micropyrometer for determining the fusibility of coal ash. These studies were undertaken with a view to adopting the micropyrometer method us a substitute or alternate to the present standard gas-furnace method, in view of the obvious advantages of greater speed, smaller ash sample, smaller laboratory space requirements, less equipment and greater comfort to the operator. However, the investigation showed that the micropyrometer type of furnace as then operated in five laboratories having this equipment could not be accepted as an alternate to the standard gas furnace, which is capable of close duplication in different laboratories, as shown in a recent colmparison between the Pittsburgh Experiment Station of the United States Bureau of Mines and the Fuel Research Station of Great Britain.2 The algebraic meau

Jan 1, 1934

The Sub-committee on Safety of the Industrial Organization Com-mittee of the Institute has been asked to cooperate with the National Safety Council, and has made certain recommendations to the Board of Directors of the Institute regarding ways and means of bringing about this cooperation. The National Safety Council has been in existence seven years. Its inception was at a meeting of the American Iron and Steel Electrical Engineers held in Milwaukee in 1912. The first annual congress was held in New York City in October, 1913, at which time the Council was definitely organized. Its membership now consists of nearly four thousand members, representing industrial plants, railroads, public utility companies, insurance companies, state labor commissions, Chambers of Commerce, manufacturers' organizations, etc. These members are in all states of the Union and in eleven foreign countries, and through them the National Safety Council reaches more than six million workers.

Jan 7, 1919

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks' and to the precipitation of second phase particles,2'3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these '(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

By T. B. Counselman, T. B.

Continuous countercurrent decantation calculations have always been a headache to the cyanide man (and the chemical engineer) because of the simultaneous equations involved. These are tedious to solve, and there is considerable opportunity for mathematical error. This paper presents a shortcut method for making these calculations, which has been in successful use for twenty years by the author, and which is particularly valuable in selecting the best of several possible flowsheets, or evaluating the effect of various assumptions.

Jan 1, 1950

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."' These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11'74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By C. M. Smith

HOWARD N. EAVENSON, acting for the last time as president of the Institute, presided at the annual business meeting on Tuesday afternoon at 4 o'clock. He spoke briefly of his visits with Local Sections last fall, and read a scholarly address on "Mineral Fuels and Civilization," scheduled for early publication in these columns. Karl Eilers presented the Treasurer's report, showing last year's income to be $134,967.44, compared with expenses of $133.266.51. Comparable figures for 1933 were $121,689.90 and $115,462.60. The Institute's peak income was in 1923 about $208,000. Newell G. Alford read the report of the Membership Committee showing 750 new members elected and placed on the rolls in 1934, compared with 328 in 1933. Losses by resignation last year were 81, compared with 262 in 1933; and 691 were suspended for non-payment of dues, compared with 747 the year before. Total membership, including 579 Student Associates, was 7742 at the end of 1934. Applications for membership have been coming in freely the last few months.

Jan 1, 1935

By S. Le Fevre

The application of electricity to the mining and beneficiation of the magnetic iron ores of the Mineville, N. Y., district, on Lake Champlain, has resulted,in economies and enhanced quality of product, without which only a comparatively small quantity of the present output could be marketed. The output of the Witherbee, Sherman & Co. mines is about 700,000 tons per annum, and of this about four-fifths is treated by magnetic separation to increase the iron content and reduce the phosphorus. The use of electricity for the magnetic separation of the ore from the gangue is therefore of primary importance, and makes possible the application of electric power for mining and preparing the ore for concentration. The fact which speaks loudest in favor of the application of electricity is this: It is possible for about 25c. per ton of shipping ore to furnish all the power required to put the ore on cars. This includes mining a hard ore underground, from a depth of 900 ft., hoisting to surface, crushing to $ or 8 in. in size, and separating from the gangue. This also includes lights about the works, and all miscellaneous power, such as about the shops. The first plant for the generation of electric power for use at Mineville was completed in 1903, and was one of the first for the application of electricity to mining iron ore. This was a Nordberg compound condensing steam engine, direct connected to a 750-kw. alternating-current generator, 3,300 volts, 3 phase, 25 cycles. All the plants added later use the same current but with higher voltage. The map, Fig. 1, shows the power plants and the transmission system; Figs. 2 and 3 are views of the shaft houses and the mills. The power from the first plant was distributed to Mills 1 and 2, one 2,500 cu. ft. compressor, and to the Harmony hoist, which was driven by a 300-h.p. motor operating four 10-ft. drums. Our experience with the hoist covers largely the development of electric hoisting from 1903 to date, and in some cases improvements were worked out to satisfy our needs. The motor is still operating as installed, but the control apparatus has been radically changed several times. When installed, the iron re-

Jan 1, 1915

By P. Eadington

I feel sure that the apparent anomolies between his findings and ours arise as a result of the different experimental methods used. The modem oxygen electrode method he used is sensitive to nano moles of oxygen uptake whereas the method we used was only sensitive to micro moles at best. Furthermore, our experimental method did not permit measurements to be made in the first ten to fifteen minutes of reaction, the very time he is observing. Direct comparison of his data to ours is made difficult because of not knowing the specific area of the samples he used. However, we found that precipitation of PbS using sodium sulphide gave rise to samples of area approximately 30 m2 g - 1. Noticing the rapid decline in oxidation rate over ten minutes, as reported in Table 1, one can conclude that we could not measure the rate after ten minutes using our method. Taking the above area I estimate that at these rates only a small fraction of surface would be oxidised in a period of hours. I can only conclude that at some point a change in oxidation mechanisms occurs giving rise to a much faster rate such as we observed. Finally, I would like to comment on the apparent inertness of the homogeneously precipitated lead sulphide sample 11. This method of preparation we found to give specific areas of 20 to 30 times less than other methods and this would account for the very low oxidation rate.

Jan 1, 1982

By Edward A. Vitunac

The emerging importance of pneumatic conveying systems for bulk materials is largely due to the economic advantages such systems frequently exhibit when compared to alternate methods. Included in these advantages are relative simplicity, ease of installation, flexibility, ease of maintenance, cleanliness, safety and ease of automation to the degree desired. In general, installed costs favor a pneumatic system when compared to competing mechanical systems if the transporting distances are long or to and from many points. In addition, supplemental use such as cooling, heating, or drying may supply the incremental value required to justify its selection.1 The main disadvantages of a pneumatic system are the greater horsepower required per unit weight of material conveyed, material limits in abrasiveness, and density. In addition, material breakage tends to increase at changes of direction and at any obstruction such as that caused by the imperfect butting of two pipe sections in the conveying line. Classification of the material at the discharge may also cause problems in dusting and segregation. Materials weighing less than 4 lb per cu ft tend to cause feeding and collecting problems although they can be conveyed easily. Material between 4 lb and 20 lb per cu ft can be handled with fewer problems, but flow rate is hard to predict. The 20-60 lb per cu ft range offers best results, whereas materials of over 60 Ib per cu ft tend to drop out of the air stream and settle in the pipeline unless careful pro- visions are made to prevent this.2

Jan 5, 1968

By P. H. Wendland

Calculations are presented for the design of a silicon photodiode in which the incident light beam makes multiple passes between the detector surfaces. Total internal reflection is used for this "light-trapping" effect. By this means, the optical path length can be extended to several millimeters, while the electrode separation remains less than 102 cm, as required for nanosecond response time. Data are presented for a Schottky barrier photodiode constructed on a multiply reflecting silicon base wafer. It is shown that the long-wavelength response is considerably extended in such structures without a corresponding sacrifice in high-speed response. The development of efficient and powerful lasers at 1.06 p has stimulated interest in detectors which operate at this wavelength. In typical silicon photodiodes, for detecting 1.06 p radiation, the requirements for high speed and high sensitivity are mutually exclusive. Since the absorption coefficient is only 25 cm-', a lo-'-cm path length is required to absorb 92 pct of the incident 1.06 p radiation. If the electrode separation is greater than 10 cm, however, the carrier transit time will be greater than 1 nsec. This problem can be solved by allowing the incident light beam to make multiple passes between the electrodes. The optical path length can then be extended to several millimeters, as required for complete absorption, while the electrode separation remains less than 10' cm, as required for nanosecond response time. In a typical photodiode geometry, one ohmic contact and one rectifying contact are formed on the two opposite surfaces of a base wafer, and the wafer thickness determines the electrode separation. The objective of the multiple reflection design is to allow all 1.06 p radiation to enter the detector front surface and to form the back detector surface so that no 1.06 radiation can exit. Total internal reflection at the back detector surface is well-suited for light trapping of 1.06 p radiation because the relatively large dielectric constant of silicon leads to a critical angle of 16.5 deg for total internal reflection. LIGHT TRAPPING It is well-known that, as light passes from one medium such as air into another medium such as glass or silicon, the angle of refraction is always less than the angle of incidence. In the limiting case, where the incident rays approach an angle of 90 deg with the normal, the refracted rays approach a fixed angle +, beyond which no refraction is possible: this is called the critical angle. It follows from Snell's law that where = critical angle, n - index of refraction of air, n' - index of refraction of the medium. Applying the principle of reversibility of light rays, all internal angles of incidence greater than +, will produce total internal reflection and "light trapping". The index of refraction of silicon at 1.06 p is 3.5,' and the critical angle is thus 16.5 deg. Fig. 1 shows these relationships for silicon. This very small critical angle in silicon is significant because all incident angles between 16.5 and 90 deg will produce total internal reflection and "light trapping". This effect can be implemented with a "prismlike" geometry, so that incident light can be introduced into the sample without loss and "trapped". PHOTOSIGNALS A precise knowledge of the absorption coefficient at 1.06 in silicon is of critical importance to the design of fast and efficient silicon photodiodes for 1.06 radiation. Dash and newman2 show a value of 25 cm-l, and our measurements have corroborated this value. Assuming that the collection of photoinduced minority carriers is perfect, the quantum efficiency of a photodiode is dependent only on the absorption coefficient. It then follows from Lambert's law that where QE is the quantum efficiency in pct, a is the absorption coefficient, d is the optical path length, and the reflectivity at the surface is assumed to be completely suppressed by an optical interference layer. Fig. 2 gives the maximum quantum efficiency for 1.06p radiation of a silicon photodiode with optical path length d, using Eq. [2]. The ultimate response time of a fully depleted photodiode to an incident light pulse can be considered to be the arrival times of all photoinduced carriers at the contacts, i.e., the minority carriers at the junction interface and the majority carriers at the oppo-

Jan 1, 1968

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.'This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

By Alfonso W. Ovalle

INTRODUCTION The block-caving mining method is one of the most economical ways existing today to extract ore from nature. It is undoubtedly the least costly of the underground systems and moreover it compares favorably to open-pit mining. In addition to its low cost characteristic, the block-caving mining method permits a great extraction volume as can be exemplified by El Teniente's output capacity of over 22 million tons of ore per year. These characteristics of block-caving give assurance that, even though it is a very old mining system, it will be a good answer to the many future large massive low ore grade deposits to come and a1 so to rep1 ace open-pi t mining as such operations get deeper with higher stripping ratios. These are the reasons that induce further study of block-caving. In this paper block-caving at El Teniente is analyzed with due consideration to the major problems that this mine will encounter. Emphasis is given to the factors influencing the mining of soft ore which accounts for most of the ore to be extracted in the next ten years. A separate paper is devoted to a major modification introduced to block-caving hard primary ore at El Teniente by means of LHD equipment extraction. DESCRIPTION OF THE PRESENT MINING Ore Production and Flow Over 62.000 tons per day of ore are extracted 359 days per year at the El Teniente Mine. The Teniente 8 train haulage level at 1.983 m takes 29.000 tons daily to the Col6n Concentrator. Two trains make the 8 km haul with 16 cars per train. Car capacity is 90 tons. The Teniente 5 train haulage level 298 m above takes 33.000 t per day to the old Sewell Concentrator. Ore is produced from three production areas in two different levels. The so called North Mine produces 42.000 tons daily from the Teniente 4 level 65 m above the Teniente 5 haulage level. The Central Mine produces 1.000 tons from the first hard rock block caved at the Te- niente 4 level. The combined 43.000 tons per day production is sent through inclined 2 m dia- meter raises to the Teniente 5 haul age level , where 33.000 tons are taken 2.5 km to the Sewell Concentrator and 9.000 tons are hauled 0.5 km to a 5 m diameter vertical ore pass which sends ore to Teniente 8. The haulage is by 7 trains, 15 gabble-bottom cars per train. Car capacity is 20 tons. The so called South Mine produces 19.000 tons per day from the Teniente 1 level 645 m above the Teniente 8 haulage level. Ore is transferred by 2 m diameter inclined raises to the Ten 1 Retram level 22 m below, where 5 trains with 20 Sandfor Day cars per train, 8 tons capacity per car, haul the ore 1.5 km to two vertical 5 m diameter ore passes which connect to Ten 8. Starting in 1982 the Central Mine will in- crease production to 6.000 tons per day. An in- dependent loop haulage system will start operat- ing at the Teniente 5 level to feed a new under- ground 1.372 mm (54 in.) gyratory crusher which will send minus 152 mm ore (9 in.) to Teniente 8. In two or three years time the North Mine will only feed the 33.000 tons to the Sewel 1 Concentrator with its old Teniente 5 haulage system. The Col6n Concentrator will be fed from the Central and South Mines. Figure 1 shows the transfer systems and ore flows. The Ore Body In plan view at the Teniente 4 level the ore body has a kidney shape 1.800 m long and between 400 to 700 m wide. The north-eastern section of the ore body was washed away by the Teniente River. At the Sub 5 Level, 125 m below Teniente 4, the mineralization completely surrounds the circular 1.000 m diameter steep-sided barren breccia pipe (Braden pipe) . The ore body rock is 73% andesite, 14% diori te, 13% dacite and 6% mineralized breccia. Most of this ore is secondary enrichment sulfides which apart from the dacite is strongly fractured being chal cocite, cove1ine , bornite and

Jan 1, 1981

By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965