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By Alfonso W. Ovalle, Héctor R. Albornoz

INTRODUCTION The El Teniente Mine of Codelco-Chi le has extracted 588 mil lion tons of ore in its 77 year history for a total copper output of 8.800.000 tons. The mine production has been obtained mainly by traditional block-caving where grizzlemen using a hand held lever send ore through long-raises to load trains. At present the mine is about to introduce mechanized block-caving using LHD equipment to extract the primary rock. This paper describes this method which will be tested starting next month by caving an 11.000 square meter block. THE PRIMARY ROCK PROBLEM The secondary enrichment sulfides of the El Teniente ore body have characteristics which makes a standard unmechanized block-caving practice very successful. In the 60's parts of blocks encountered primary ow in the Teniente 1 and Sub-13 levels which proved to be extremely hard to extract. These foretold the obstacles that arised in the central part of the Teniente 4 level. Preparation of a completely primary 8.100 square meter block started in 1970. Its undercutting was completed by the end of 1972 and by 1973 the problem of mining the primary rock was clearly visualized. The numbers below describe the difficulties in mining this block: -Long-hole drilling rate is 90 m (270 ft) per shift in secondary rock and 37 m (110 ft) in primary. - Undercutting which is completed in 9 shifts in secondary took 180 shifts in the primary block. - Average grizzlymen productivity in secondary is 250 tons per shift while in primary it is only 25-30 tons, both at 343 mm (13 1/2 in. ) grizzly opening. - Powder consumption for secondary blasting increased from 8 grams per ton in secondary to 84 in primary. - The protection pillar between the under- cutting and the production levels was 60% broken in primary while 20% is usual for secondary. - Extraction advanced 5 cm per day in primary while a 50 cm per day rate is the aver- age in secondary. This is the main reason that after 8 years this primary block has a 20% extraction. Secondary blocks take 1.5 to 3 years to complete their extraction. - 80% of the boulders in primary rock are larger than 343 m (13 1/2 in.) with 10-20 % of them larger than 3 meters. -Direct cost of production (preparation, undercutting, extraction and haulage), using the traditional block-caving design for secondary rock, increased 3.5 to 4 times when used in primary rock. The following indicators of Table 1 show the rock characteristics differences.

Jan 1, 1981

By William L. Fink, Kent R. Van Horn

Zinc is one of the effective elements introduced to enhance the strength of aluminum. This strengthening is principally attributable to the high solid solubility of zinc in aluminum and the pronounced variation of solubility with temperature. Consequently an accurate determination of the solid solubility curve is desirable. The solid solubility relations have been studied by numerous investigators. Shepherd1 first established the existence of a solid solution region at the aluminum end of the diagram (-v phase) by specific volume and microscopic determinations. Bauer and Voge12 published a constitutional diagram which showed the limits of solid solubility as determined by thermal and microscopic methods. Hanson and Gayler3 presented the aluminum-zinc diagram which is now most generally accepted (Fig. 1). Chill-cast samples were given thermal treatments designed to obtain equilibrium conditions, quenched, and microscopically examined. The solubility was placed between 15 to 20 per cent at 60" C., 20 to 22 per cent at 140" C. and 36 to 38 per cent at 270" C. Sander and Meissner decidedly modified the limits of the -y phase field of Hanson and Gayler's diagram by using similar methods on chill-cast specimens annealed for a shorter period of time. Tanabe,s utilizing dynamic hard-ness, electrical conductivity and dilatometric measurements of specimens at temperature, obtained values comparable to Hanson and Gayler's at room temperature, but appreciably lower at higher temperatures. Nishimura6 concluded from age-hardening results of aluminum-zinc alloy chill castings, which had been quenched from 400" to 500" C., that the solubility of zinc in aluminum at room temperature is less than 5 * Metallurgical Division, Aluminum Research Laboratories. 1 E. S. Shepherd: Aluminum-Zinc Alloys, Jnl, phys. Chem. (1905) 9, 504. 2 0. Bauer and 0. Vogel: Aluminum-Zinc Alloys, Int. Jn1. Melallog. (1916) 8, 101. 3 D. Hanson and M. V. L. Gayler: A Further Study of the Alloys of Aluminum and Zinc. Jnl. Inst. Met. (1922) 27, 267. 4 W. Sander and K. L. Meissner: ZII~ Kenntnis der Konstitution der Aluminium-Zinklegierungen. Ztsch. f. Metallkunde (1922) 14, 385. 4 T. Tanabe: Studies in the Aluminum-Zinc System, Jnl. Inst. Met. (1924) 32, 415 6 H. Nishimura: On the Age-Hardening of Aluminum-Rich Al-Zn Alloys. Mem. Kyoto Imp. Univ. (1924) 3, 133.

Jan 1, 1932

By P. H. Dudley

The present paper was suggested by the paper read by Mr. R. W. Hunt at the New York Meeting, in February last, on rail-sections (Trans., xvii., p. 778)) in the discussion of which I brought forward some of the facts and observations here stated. Professional duties having prevented me from writing out my part of that discussion in time for its publication in the volume containing Mr. Hunt's paper, I take the opportunity to present it in separate form and greater fulness. The striking features of the series of rail-sections submitted by Mr. Hunt are their shallow heads and heavy bases. In these respects they are quite similar to the section of the 80-1b. rail, which I designed in 1883 to meet the requirements of the traffic of the New York Central and Hudson River Railroad. Before the adoption of the 80-1b. rail, this road had modified its 65-1b. section from a shallow head with rounding sides and quite heavy base to one having a deep head and thin base. All the leading railroads had changed from the earlier sections of steel rails to those having deep heads and thin bases, conforming to the recommendations of the Committee on Rails of the American Society of Civil Engineers. It is but proper to say that the committee's investigations upon the wear of rails were made upon the rails manufactured under a practice quite different from that which obtained after the committee's recommendations were carried into effect. The results in actual service have been contrary to what was expected. Fig. 1 shows my 80-1b. section of 1883. Before designing this rail I had taken, at different times, a series of diagrams of the condition of tracks, with my car, on the New York Central and Hudson River Railroad, all of the New England railroads, and all but one of the trunk lines. My diagrams gave me an opportunity which could not otherwise have been obtained to see the wear of great numbers of sections of rails under widely varying conditions of traffic.

Jan 1, 1890

By Norman B. Pilling

Practical limitations to the usefulness of silicon steels are the hardness and brittleness silicon imparts to iron, making iron-silicon alloys of more than 8 per cent. silicon content unusable except where castings can be employed. In the use of commercial silicon steel, in thin rolled sheets, as in transformer construction, when the silicon content exceeds 4.2 per cent. the sheet is too brittle for satisfactory shaping by punching or similar operations. When such a brittle steel is sheared, it frequently breaks along a haphazard path in advance of the cutting tool. In Fig. 1 is shown a slightly enlarged view of the sheared edge of a 14-mil enameled sheet of nominally 4 per cent. silicon steel. In 5 in. along the sheared edge, only 44 per cent. was actually cut; the rest was torn, with the path of fracture varying widely from the path of travel between the shears. This is probably an extreme case of such brittle-ness, but a shearing or punching test is not necessary to reveal brittle-ness of this order; narrow strips will break when bent between the fingers. In Fig. 2, the proportion of actual cut edge is greater, but secondary fractures branch off at about 30" from the line of shearing in advance of the cut. Deprived of the support of adjacent parts of the sheet, the tips of the angles are bent out of the plane of the sheet by the shears, leaving a peculiar flared effect, like the set of the teeth on a saw. An end-on

Jan 1, 1923

By J. C. Febles

HISTORY. THE use of iron for the precipitation of copper was known at least as early as the fifteenth century. Both Paracelsus and Basil Valentine refer to it in their writings, as early as 1500 A. D. It was used in Peru, for this purpose prior to 1637, and at Rio Tinto, Spain, as early as the sixteenth century. The statement has been made repeatedly that in the early history of the mining industry at Butte, the practicability of this method of recovering copper from solution was overlooked, and that enormous quantities of copper-bearing water were allowed to go to waste, the copper in which might easily have been recovered at small cost; and that this oversight on the part of the mine operators was due to ignorance of this method of recovering copper. As a matter of fact, very little copper-bearing mineral was encountered in the mines of Butte until a depth of 400 or 500 ft. bad been reached, and in many cases much greater depths were necessary to reach the copper-bearing zone. The water encountered in the upper levels (although in most cases quite highly mineralized) contained little or no copper, and it was only after considerable areas of copper-bearing ore had been uncovered and developed that copper sulphate began to. appear in the mine water in any considerable quantity. In fact, the first water that was observed to contain copper carried it in such small amounts as to be of little or no importance. It was only after years of underground work had opened extensive areas of stopes, drifts, and other underground workings, these being subsequently filled with waste, nearly all of which contained small copper values, which became oxidized by exposure to the air and were acted upon by the slowly percolating mineral water, that the recovery of copper from mine water became commercially important.

Jan 7, 1913

By M. S. King

In the design of foundations for large structures and of safe mine openings in rock, the results of laboratory and small-scale in-situ tests are often used to predict the behavior of the material as a whole. For reasons of simplicity in these analyses, the rock is usually treated as an ideally elastic, isotropic material. It has been observed, however, that most rocks are neither isotropic nor ideally elastic. This observation is particularly true for rocks subjected to low confining pressures. It is therefore necessary to investigate further the effects of anisotropy and nonlinearity on the mechanical behavior of rocks. When small differences in stress and strain only are involved, the rock may be treated as an elastic material. The elastic constants for such a material subjected to a particular confining pressure can be calculated from the classical theory of elasticity for different degrees of anisotropy. There are two experimental methods by which this can be done: first, from measurements of static stress-strain relationships; second, from elastic wave velocities measured in the rock. The former yields the static elastic constants, and the latter, the dynamic constants. The static constants will be equal in magnitude to the corresponding dynamic constants only if the rock is ideally elastic. Walsh and Brace1 have reviewed theoretical studies of the elasticity of rock considered as a material containing pores and cracks. They re- ported that the presence of sharp, narrow cavities at low confining pressures strongly influences the mechanical properties of a rock. A considerable reduction in magnitude of elastic moduli is associated with the presence of inhomogeneities such as cracks or joints. The elastic properties appear to approach those of the uncracked material in magnitude as the cavities are closed by higher pressures. Walsh and Brace

Jan 1, 1970

By Stanley Herold

Considerable interest has been shown, during recent years, in the possibilities of developing oil fields in the South American Republics, now that the exhaustion of our present fields can be seen in the not very distant future. The demand for fuel oil and its products has been increasing far more rapidly than our increment of production during the last few years. Increase of consumption has been largely curtailed by the lack of sufficient supply. The main factors that have contributed to our previous neglect of the southern fields have been as follows:, (a) Lack of sufficient demand for the product. (b) Competition with producing fields, having large production, low cost, and better geographical position, such as Tampico, Mexico. (c) Greater interest in home fields with ready market at hand. (d) Our ignorance of southern economic and geologic conditions, clue to the distance between those areas and our financial centers. (e) Economic conditions in the southern countries, necessitating high costs of exploration and exploitation of the fields.

Jan 9, 1918

Joseph E. Thropp, Jr., Indiana Harbor, Ind.:—To what do you attribute the fact that in some localities the by-product coke sells at a premium over the ordinary bee-hive coke for foundry use ? If the cell-structure is preferably soft and rather thick in coke for foundry use, as I understand it, do you mean that by-product coke has soft and thick cell-walls ? William H. Blauvelt, Syracuse, N. Y.:—As I say in one of the paragraphs of my paper, the tendency seems to be towards the manufacture of foundry- and furnace-coke under somewhat different conditions. The development of the best cell-structure in coke, of course, has not reached perfection, but we are making progress, and we are inclined to believe that under ordinary conditions the best furnace-coke, that is, coke with the hard cell-wall and the well-developed cell, is produced at fast coking-time and high heats, whereas the best foundry-coke seems to be produced at somewhat lower heats. In one of our plants we are making furnace-coke in 16-hr. coking-time, and foundry-coke in 20-hr. time. Foundry-men want the strong, tough coke. I think the furnace-men present will agree that the best furnace-practice requires a hard coke, with a well-developed cell-structure. Replying to the question as to the reason for higher prices being realized for by-product foundry-coke than for bee-hive coke, of course, the immediate reason is that it suits the foundry-men better. Perhaps one cause may be that we are able, by the selection of coals, which is not usually practicable at bee-hive plants, to get a quality and analysis best suited to foundry-work, with high carbon-content, and with cell-structure and physical strength especially suited to the foundry-men's ideas.

Jan 1, 1913

By Gustaf Ising

For relative gravity measurements, the author in 1918 described an instrument1 of which the essential part consists of a highly astatized, standing pendulum turning about a horizontal elastic axis. This type of instrument has been used recently in practical field work, therefore a description of its principle and technical development is given herein. Part I, describing the principle, is a direct translation of the original Swedish paper.l Part II gives an account of the practical elaboration of the instrument, together with some description of measurements performed. I. Principle of Using Astatized Pendulums1 In order to reduce the trouble and waste of time attending the use of ordinary pendulums in measuring the force of gravity, various instruments of another type have been suggested for relative determinations, as a rule arranged in such a way that the attraction of the earth on a certain body or mass of fluid is balanced by elastic force from a spring or a shut-in mass of gas. A change in the force of gravity is then made manifest as a change in the position of equilibrium of the body, in that the deformation of the spring (or compression of the gas) is changed. With such instruments there are, however, great difficulties in keeping the elastic force constant or its variation known with sufficient exactitude, because of elastic after-working, influence of temperature, and so on. The author suggests for relative determinations of gravity another type of instrument, in which two directional forces (control coefficients) rather than two forces are compared with one another. By "directional force" or "control coefficient" is meant that quantity in a rotatable system that, multiplied by the angle of deflection, indicates the moment counteracting the deflection. In this way it will be possible greatly to reduce the influence of the elastic after-working, which in instruments with spring devices acts so disturbingly. The instrument is made with a rotatable system arranged in such a way that the total control coefficient acting upon it, is composed

Jan 1, 1940

By Pradeep K. Rohatgi, Clyde M. Adams

Structures obtained on freezing of several hypo-and hypereutectic Al-Cu alloys over a range of solidification rates have been examined. Dendrite spacing, L, increases linearly with solute concentration and with the square root of the inverse freezing rate. The relationship for hypoeutectic alloys is: where rate of change of fraction solid with time, is freezing rate, C is solute concentration, (pct Cu)=1. Mass transport in inter dendritic liquid during solidification is analyzed; the experimental observations suggest maximum concentration differences and constitutional supercooling in the inter dendritic liquid increase with an increase in the solute concentration. The dendrite morphology changes with freezing rate and alloy composition. The dendrites of the a phase are parallel, uniformly spaced plates with slow freezing and rods with rapid freezing. Nonor-thogonal side branching has been observed in phases with cubic and tetragonal structures. Side branches in a dendrites are orthogonal with slow freezing and at 60 deg with rapid freezing. Formation of second-phase envelopes around the Primary phase is also discussed. DENDRITIC structure is characteristic of many types of phase transformation. The most extensively studied so far has been solidification of liquid solutions. chalmersl and coworkers have interpreted the formation of dendrites in terms of the breakdown of a planar interface. Most of the work done concerns itself with the development of an instability at the interface. Little theoretical work has been done quantitatively to relate the parameters of dendritic structure to mass transport in the liquid phase. A few empirical relations based on the experimental2'3 observations exist in the literature. Several workers2 including Brown and Adams1 have studied dendrite spacing in A1-Cu system as a function of solidification variables. In most cases, dendrite spacing has been found to increase linearly with the square root of some parameter proportional to the freezing time. The effect of solute concentration is not clear; some workers report the dendrite spacing increases with solute concentration4 whereas others report vice versa.''' ~ohatgi' has observed an increase in the spacing between ice dendrites with an increase in solute concentration in water. Tiller has also suggested that dendrite spacing should increase with solute concentration. In the present work dendrite spacing and morphology have been examined as a function of solute concentration and freezing rate. The freezing rate is defined as the fraction of liquid solidified per unit time, dfs/dß?, where f, is the fraction solid and 8 the time. The fastest freezing rate studied was 4550 times the slowest freezing rate. THEORETICAL CONSIDERATIONS It is of interest to analyze the concentration distribution in the liquid phase between growing dendrites during solidification, Fig. 1. Since this distribution is a direct consequence of the rejection of solute by the growing solid, a diffusional process, the concentration gradients increase with the freezing rate. However, when solidification rate is the only variable in a series of experiments, the interdendritic liquid regions become smaller (i.e., the dendrites become more closely spaced) with an increase in freezing rate. The main purpose of the analytical treatment of interdendritic liquid diffusion will be to reveal a tendency for dendrite spacing to decrease with increasing solidification rate in just such a way that the maximum concentration differences developed in the liquid phase are remarkably independent of freezing rate. Two rather different analyses are set forth, one pertaining to the one-dimensional diffusion which obtains in the interdendritic liquid between parallel plate-shaped dendrites, and the other to the cylindrically symmetrical diffusion around rod-shaped dendrites during early stages of solidification. The results of the two analyses are quantitatively similar, correlating dendrite spacing, maximum concentration difference, and freezing rate. First consider the simpler one-dimensional case. Two parallel plate-shaped dendrites are separated by a distance, L, between centers, Fig. 1. Solidification takes place by the thickening of these plates, with solute being rejected into the liquid. It is assumed there is no diffusion in the solid. This thickening process is slow enough and the dendrite spacing small enough that the concentration differences which develop, although interesting and important, are very small (an important assumption which is verified ex-

Jan 1, 1968

By Augustus Locke

The paper has two parts: the field argument and the microscopic argument. The field argument indicates that either the deep chalcocite has replacea sulfide of extraordinarily easy replaceability or it is hypogene. The microscopic argumentindicates that this sulfide, if it existed, must have been hypogene bornite; that this bornite must so excel known bornite in replaceability as to constitute a new variety; that the existence of this new variety is wholly unsupported by evidence; and that the deep Butte chalcocite is therefore hypogene. IN 1900, when the public first heard of "secondary enrichment" the Butte chalcocite seemed clearly supergene. Mining, through successive regions of leached capping, bonanza sulfide, and sulfide less rich, had paused at lean bottom levels which, though chalcocite-bearing, suggested the waning of copper. The deepest chalcocite, at 1500 ft., was yet too shallow to disturb the supergene hypothesis. But, with deeper mining, lean levels yielded to fat ones. Here and there they showed, within the same vein, an inverted distribution, chalcopyrite above and chalcocite below. To the miners' astonishment, they carried chalcocite, unaffected by cross faults, on an independent course to the depth of 2500 ft. The pattern of ore distribution, hitherto revealed only in fragments, was now appearing in perspective, and, in the depth of the chalcocite, was beginning to make Butte differ from all districts where the chalcocite is indubitably supergene. The idea of hypogene origin at length came into favor; by 1913, when Sales1 advocated this origin, the argument had become a powerful one. This argument rested on field evidence; but, already, there was beginning to emerge microscopic evidence not included in this arugment. Especially pertinent was the proof that (1) The deep chalcocite lies in-mixed with bornite, often microscopic; (2) the deep chalcocite often replaces bornite; and (3) replacement of bornite by chalcocite is accom-

Jan 3, 1924

By C. E. Birchenall, G. Derge

IN studying the kinetics of slag-metal reactions, it has become increasingly apparent that a complete knowledge of all aspects of interface phenomena will be required to clarify these processes adequately. A part of the data required for all oxidizing slags used in the refining of impure iron to steel is the rate of exchange of iron between the slag and metal phases. The simplest equilibrium of this type is that between liquid iron and iron silicate slag when both phases are equilibrated with the silica crucible containing them. In this study, the exchange of iron between the two liquid phases has been measured by using radioactive Fe as tracer. The observed high exchange rate indicates the ease with which such interfaces may be crossed in refining processes. The experiments required for this study involved relatively minor and normal modifications of well established techniques. Melting was accomplished by induction heating in heavy walled, fused silica, rotating crucibles." Rotation was used to minimize dilution of the slag by crucible erosion. The melting stock was ingot iron. Slags were prefused in iron crucibles using chemically pure grade oxide reagents. The special conditions applying to the active iron additions will be described for individual experiments. Suitable precautions were observed with regard to protection against radiation hazards.' Identification of Activity This particular study was initiated several years ago, but held in abeyance because the radioactive iron available at that time contained a foreign activity which concentrated in the slag so as to mask the iron activity and render the results unin-terpretable. With the benefit of experiences from other studies, radioiron of suitable purity can now be prepared. As received from the Isotope Div. of A.E.C., the unit appears to contain Fe + Fe50 and a high activity cobalt. The cobalt and iron are separated by repeated ether extractions, and the purified iron stored for sufficient time for the Fe'7 44 day half-life) to decay to negligible activity, leaving only Fe as the active isotope. This was confirmed by the absorption curves for slag and metal samples from heat No. 1. In Fig. 1 the experimentally measured points for the absorption curves of slag and metal are fitted by the calculated slope of 5.8 mg per sq cm in aluminum, which corresponds to the Mn K doublet emission resulting from the capture of an orbital electron of Fe" by the nucleus. This shows that the radioactive species are the same in both slag and metal and identifies it as Fe55 Description of Individual Heats For the first heat, the radioactive iron was contained in the prefused slag. The active Fe55 had been precipitated with carrier and was added as Fe2O3 during fusion in the iron crucible. The charge of 500 grams of ingot iron was melted, the protective iron sleeve added, rotation started, and a prefused, inactive slag was added to allow the system to approach equilibrium. After about 5 min at temperature, the wash slag was skimmed and the active slag added. Initial slag and metal samples were taken as soon as the slag was molten. Additional samples were taken at indicated intervals thereafter. Slag samples were dipped with a small iron spoon and metal samples were sucked into 1/4 in. ID silica tubes. The slag and metal samples were pulverized and mounted for radioactive counting. The slag samples were analyzed chemically for FeO. Temperature was read after the last slag sample by immersion of a Pt-Pt-Rh thermocouple protected by a fused silica sheath. Since no significant variation of rate with temperature was observed

Jan 1, 1954

By J. L. Carne

ORE control is a matter of planning and supervision based on a foreknowledge of the content and distribution of ore. The Inspiration orebody is predominately a copper-sulphide blanket, overlain by an oxidized zone of copper silicates, copper carbonates, and barren capping. Most of the ore is treated by leaching, and the optimum requirement of this method is the goal toward which the mining schedule is aimed. Both open-pit operations and underground mining are used. The problems of ore control at Inspiration are: 1-maintenance of metallurgical balance, 2-conservation of oxide ore, and 3-mining out of the orebody at an average grade which parallels that of the reserve figure. Prior to the fall of 1926 all of the Inspiration division ores were treated by flotation, but the mixed ores of the Live Oak-Keystone section carried too large a proportion of copper in the form of chrysocolla for satisfactory flotation. For this type of mixed ore the leaching process now in use had been worked out, and the plant was put into operation in the fall of 1926. The process is known as the ferric sulphate leach, and the leaching solvents contain both ferric sulphate and free sulphuric acid. Sulphide copper in the form of chalcocite is leached by the ferric sulphate, and the oxidized copper minerals are dissolved by the sulphuric acid. From the beginning of operations to the present time the plant has treated some 67 thousand tons of ore having an average copper content of 1.142 pet, of which 0.605 pct has been in the form of oxidized copper minerals. The plant is currently being operated at the rate of 11,500 tons per day, 7 days per week. However, this tonnage is produced in 6 days of mine operation. The average current grade is approximately 1 pct copper, of which about 50 pct is present as oxidized or acid-soluble copper. Close control of metallurgical procedures is a vital factor in operation of the plant and is in turn dependent upon careful regulation of feed. An excess of sulphide copper requires the presence of more ferric sulphate in the leaching solvents. On the other hand, an excess of ferric sulphate in the presence of a low sulphide feed seriously reduces the efficiency of electrolytic precipitation in tank house operations. This condition must be avoided at all costs. An additional factor must be considered. It is known that the sulphide content is predominant in the ore which remains in the reserve. To maintain the necessary sulphide-oxide proportion, so that the entire reserve will mine out at both a grade and a sulphide-oxide ratio that will be permissible throughout the remaining life of the property, it is obvious that the oxide reserve must be currently preserved to as great an extent as possible. Fortunately much of the oxide reserve is found in the open-pit operation. This happy circumstance adds flexibility to the procedure and makes it possible to maintain the close regulation necessary to insure best overall results, both mining and metallurgical. The two ore streams from the pit and underground operations join at the coarse-crushing plant, and proper control must be exercised before the ore reaches this point. The open pit is currently providing about 55 pet of the ore and underground operations the balance of production. Both operations are under a single superintendent so that the closely interrelated problems may be more readily controlled. The least flexible of the two producing units is the underground mine, where the mining method is block caving. Although a block of ground may be undercut and developed, characteristics of the material determine its caving action. The ore in the chutes must be drawn. The area currently mined from underground is in a zone predominately sulphide and is generally

Jan 1, 1952

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins' and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer' type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The mechanical properties of Ti-C and Ti-C-0 alloys can be altered by heat treatments to dissolve or reject carbon from solid solutions. The maximum strength is obtained by annealing just below the peritectoid temperature. Quenching from the ß-carbide field results in softening. Impact behavior is influenced by the extent of solution of interstitials CARBON is not as important in titanium alloys as it was in earlier years when graphite induction melting was more prevalent. With induction melting, carbon pickup is about 0.5 to 0.8 pct. Cold-mold arc melting with graphite electrodes, which is among the more current methods, results in carbon pickup of 0.1 to 0.2 pct. The titanium-sponge melting stock itself contains about 0.02 to 0.07 pct C, picked up from the magnesium used in the reduction process. Thus, carbon is still one of the more important contaminants in titanium and needs careful study and evaluation in order to understand titanium and titanium alloys. Moreover, it is equally proper to consider carbon as an alloying addition because, in controlled amounts in titanium alloys, it may serve a most useful function. This is particularly the case where the ultimate in toughness is not required. The addition of carbon to titanium results in a peritectoid-type system as illustrated in Fig. 1. The solubility of carbon is seen to be higher in the a phase than in the ß phase in the temperature range of interest. Below the peritectoid temperature, the solubility of carbon in a titanium decreases with decreasing temperature. This type of system permits many microstructural and heat-treatment variations which may influence the properties of the alloys. The study of how the microstructure variations affect mechanical properties is described in this paper. Experimental Procedures The experimental techniques and testing methods used in this work were the same as those described in detail in a previous paper.' No further descriptions will be given except where changes have been made. High purity iodide titanium, produced by the New Jersey Zinc Co., was used in all of the alloys. Carbon additions were made using high purity spectro-graphic carbon electrodes in order to obtain the highest purity carbon available. The alloys were prepared by double arc melting to reduce the possibility of segregation. The alloys were forged at 875°C to ¾ in. round, descaled, vacuum annealed for 5 hr at 900°C to remove the residual hydrogen, and swaged to ¼ in. round at 750°C. All heat treatments were made on material in this initial condition. Two of the early Ti-C ingots were found to have been contaminated in melting. Vacuum-fusion analyses showed that the two contaminated alloys had picked up oxygen, so the test results on these two alloys permitted an evaluation of ternary Ti-C-0 alloys. A list of the alloys and their compositions are given in Table I. Properties of Ti-C Alloys In a peritectoid-type system, such as the Ti-C system, the chief microstructural variable which influences the properties is solid-solution strengthening. For a given composition, it is possible to control the disposition of carbon, either in solid solution or as the compound Tic, by suitable heat treatments. When in solid solution, the carbon present in the alloy makes a definite contribution to the strength of the alloy. However, when present as Tic, it has very little effect on the strength. Other microstructural variables considered in this investigation were transformation structures and grain size. As discussed in subsequent sections, these variables have only a minor effect on properties as compared to the solid-solution effect. Solid-Solution Strengthening: The principal strengthening mechanism for Ti-C alloys has been found to be solid-solution strengthening. Carbon in interstitial solid solution strengthens titanium, but has very little strengthening effect if present as the compound. Since carbon has a higher solubility in

Jan 1, 1956

By Vito J. Colangelo

The primary object of this study was to determine the effect of ferrite and its orientation upon the mechanical properties of a precipitation -hardening stainless steel with particular attention to the short-transverse properties. The investigation consisted of Jour major parts : the preliminary investigation of billet properties, the effect of forging reduction and ferrite content upon mechanical properties, the effect of notch orientation upon impact strength, and the relationship of heat composition to ferrite content. Low ductility and impact strength in the short transverse direction were found to he associated with the orientation and shape of- the ferrite plates. It was also determined that impact strength varied with notch orientation. The test values obtained with the notch perpendicular to the plane of the ferrite plate were lower than those obtained in the notch-parallel condition. The over-all investigation showed that high ferrite contents in general had a deleterious effect upon mechanical properties and that the ferrite content could he minimized by exercising rigorous control of the heat composition. A careful balance of elements, nitrogen in particular, must he maintained in order to reduce the formation of ferrite. THE precipitation-hardening stainless steels were developed to fulfill a need for high-strength corrosion-resistant alloys. In the annealed condition they are soft and ductile and possess many of the desirable characteristics of the austenitic stainless steels. In the hardened condition, the alloys exhibit the high strength and hardness of the martensitic stainless steels. The alloy under consideration in this investigation has a nominal composition as follows: C Mn Si Cr Ni Mo N 0.13 0.95 0.25 15.50 4.30 2.75 0.10 The hardening mechanism is identical to that of other hardenable steels in that it depends upon the transformation of austenite to martensite. This alloy because of its annealed structure and its ability to be hardened combines the desirable forming and corrosion properties of the austenitic grades with the high hardness and strength levels attainable with the hardenable grades. The reason for this apparent duplicity of proper- ties can be explained by considering a basic metallurgical difference between the hardenable stainless steels and those of the austenitic group. Both types are austenitic at 1800°F but, while the martensitic grades transform to martensite upon rapid cooling to room temperature, the austenitic grades remain austenitic even when cooled to temperatures below room temperature. The major difference then is in the degree of austenite stability. This stability can quantitatively be described by the Ms temperature. The Ms is defined as that temperature at which austenite begins to transform to martensite. The austenitic grades for example may be cooled to -300°F without producing significant quantities of martensite. The hardenable stainless steels on the other hand have an Ms temperature in the vicinity of 400" to 700°F. In cooling to room temperature, these alloys traverse the entire Ms-Mf range and show almost complete transformation to martensite. The semiaustenitic stainless steel, however, occupies an intermediate position with respect to its austenite stability. The analysis is so balanced that the Ills temperature lies at or slightly above room temperature. The resulting alloy retains much of its austenite at room temperature and yet responds to hardening heat treatments. Achieving this delicate balance of elements is therefore of great importance. Slight imbalances of the equivalent Cr-Ni ratios frequently result in the presence of 6 ferrite. It is the effects of this ferrit with which we are concerned, more specifically the effect of the quantity and ferrite orientation upon mechanical properties, particularly ductility. PROCEDURE A) Preliminary Investigation of Billet and Forging Properties. In order to determine the effect of ferrite on billet properties, billet stock from three heats with various ferrite contents was utilized. Tensile specimens were obtained in the transverse and longitudinal directions from this material and heat-treated as shown in Tables I and 11. Forgings were made from these same heats, the purpose being to determine what effect, if any, the ferrite might have upon the mechanical properties. These forgings were made in such a manner as to elongate the ferrite in the longitudinal and transverse directions. The method of forging was as follows. A section was cut from a 6-in.-sq billet of Heat A and flat-forged to 1-1/2 in. thick. Working was done from one direction only with no edging passes as shown

Jan 1, 1965

By Harry V. Welch

This paper presents a brief discussion of numerous devices and processes which have been utilized for the recovery of values from gases in copper reduction works and describes in greater detail the development and application in recent years of electrical precipitation, more familiarly known as the Cottrell process, to the problems of dust losses with furnace gases in copper-smelting and refining plants. The field for collection of suspended particles in gases is widely extended in our modern complex, congested .and industrialized mode of living, and its satisfactory solution is required by our increasing appreciation of the extravagant waste, unhealthful effects and nuisance which such uncontrolled emission of solid suspensions represents. Much of the special dust-recovery equipment in use today has been developed in one industry and carried over to many others. The early work of Cottrell was with sulfuric acid mists, aimed at the purification problem in contact acid manufacture, but the present uses of Cottrell equipment cover a diversified field—carbon black, combustible gas, oil mists, iron blastfurnace fumes and dusts, cement-kiln gases, as well as the purification of gases in contact and chamber acid plants and its wide and extended use in the nonferrous metallurgical field of copper, zinc and lead, and their associated metals. Dust and fume collection from furnace gases became a problem only with the modern development of large and amply powered auxiliary furnace equipment, which in turn permitted large furnace units, fast driving and large outputs of finished product per unit of furnace capacity. The ancient metallurgist with his small clay pot and hand-operated bellows had too little gas velocity to cause a real dust loss. As furnaces grew in size, flues and stacks were added, and undoubtedly the first observable dust losses were indicated by the deposits in the flue and stack base. Large flues, it was noted, collected more than smaller ones, and the expansion of a portion of the flue into a chamber represented the first serious attempt at recovery of furnace dust losses. For a century or more the settling chamber represented the best of skilled metallurgical practice in recovery of furnace dust, and it may be said to have reached

Jan 1, 1934

By D. A. Thomas, E. S. Meieran

Tungsten wires were examined by transmission electron microscopy after drawing and after high-temperature annealing. Drawn wire consists of highly elongated grains called fibers, whose long axis is parallel to [110]. Each fiber is ribbon-shaped, with the wide dimension of the ribbon parallel to (001) and the narrow dimension parallel to (110). Furthermore, most fibers are bent about [I10] and twisted along their length. The fibers are divided into cells, which in some cases contain a platelet substructure lying on (110) planes. The misorien-tations of these platelets accumulate to allow the macroscopic twist of the fibers. During annealing, several competing reactions occur, starting at different temperatures and progressing at different rates. Among these processes are fiber-boz~ndary migration, polygonization, dislocation rearrangement, and possibly impurity segregation. The fiber-boundary migration accompanied by the formation of transverse boundaries during polygonization leads to an equiaxed grain structure although recrystal-lization does not occur. There is a relationship between the flow stress of the wires and their average subgrain width in the form sy = s0 + kyd-1/2 . Also, there appears to be a relatio'nship between wire ductility and the formation of transverse boundaries during annealing at about 800°C. THERE have been many investigations of the structures and properties of tungsten wires1-4 due to their commercial importance for use as lamp filaments. The structural studies have so far been limited to optical microscope and replica electron-microscope studies. due to the difficulty of .-me- paring from wires thin foils which can be examined by transmission electron microscopy. However, this difficulty has been recently overcome,5 and it is now possible to examine tungsten wires by transmission electron microscopy as well as by other techniques. In this paper, the structure of drawn tungsten wire is described, as are the changes in the structure during high-temperature annealing. Some discussion of the relationship between structures and properties is also given. EXPERIMENTAL MATERIALS AND PROCEDURES Commercial 0.030-in.-diam doped tungsten wires drawn at progressively decreasing temperatures between about 1400° and about 800°C were examined. The composition, mechanical properties, and optical microstructures are described in detail elsewhere.' All experimental materials were vacuum-annealed for 10 ot 30 min at temperatures at 100°C intervals between 700° and 2000°C. Specimens were thinned for examination in the Siemens Elmiskop I electron microscope by the method of Meieran and Thomas.5 STRUCTURE OF AS-DRAWN WIRE The optical microstructure of as-drawn tungsten wire has been described by Peck and Thomas.7 They observed that wire in longitudinal section consists of highly elongated grains called fibers whose width varies between 1 and 10 µ, while in transverse section the fibers appear to be elliptical in cross section and bent about their common [110] wire axis. They explained this unusual appearance as being due to the drawing of a bcc material with a [110] texture, and predicted that the wide and narrow planes of the fiber cross section would be parallel to (001) and (110), respectively. The fibers apparently bend about the [110] axis during drawing to maintain grain boundary continuity during drawing. Transmission electron microscopy offers a way of checking these predictions as well as providing a more detailed picture of the wire structure. Figs. 1, 2, and 3 are typical electron micrographs of

Jan 1, 1965

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952

By H. A. Schwartz, W. Kenneth Bock

In this paper it is shown that when the tensile strength of a given steel in various states of heat-treatment is plotted against its elongation, a straight line results. The equation of this straight line can be computed with considerable accuracy from its chemical composition. The appropriate equations are given. The logarithm of the slope of the tensile-strength locus is shown to be proportional to the cumulative effect of the total alloy addition and the vosition of the line to be directly proportional to the cumulative effect of the alloy content. It is further pointed out that heat-treatment is more effective than composition in determining yield ratio. The latter enters mainly by its effect on hardenability, which is briefly discussed. Reduction of area and Brinell number are given some incidental attention. The data are applicable only to steels that have been normalized and/or quenched. The steels, if normalized, may or may not have been tempered. If quenched they must have been tempered at or above 4oo°C. (75o°F.). Introduction Cast steels vary in composition and frequently are used in various states of heat-treatment. It is obviously important to be able to predict the compositions that might accompany specific engineering properties by suitable selection of heat-treatments. For cast steels, which are of necessity produced heat by heat in accordance with the particular requirements of the castings to be poured, there has been, happily, much less tendency to standardization than for rolled products, whose destination is not necessarily known when particular ingots are made or rolled. It is of distinct advantage to the steel foundry-men to be able to make steel of given properties, using alloys that can be recovered from scrap, or most conveniently or cheaply bought, rather than a particular formula adopted in the interest of standardization. The heat-treatment appropriate to securing a given result in a given steel is well known to be closely related to composition. For example, molybdenum steels are not much softened by tempering except at rather high temperatures. Highly alloyed steels are "air-hardening," and on cooling in air behave like carbon steels that have been quenched. With these matters, we do not concern ourselves in this paper, although we recognize their importance. The entire picture evidently will be very complex and can be brought within accurate understanding only if our knowledge of test results can be coordinated in terms of general principles.

Jan 1, 1944