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By W. Barbarowicz, H. E. Uhland

AT the Noralyn mine and mill of International Minerals & Chemical Corp. in Bartow, Fla., process instrumentation has been incorporated in three departments-mining, flotation, and preparation. Use of the dragline is the most difficult aspect of the mining operation to control automatically. At the Noralyn mine there are two draglines, a Bucyrus-Erie 1250-B with 29-yd bucket and 235-ft boom and a Bucyrus-Erie 1150-B with 21-yd bucket and 215-ft boom. These are equipped with a minimum number of instruments, but further instrumentation would increase the operator's efficiency.

Jan 7, 1957

By R. L. Smith, J. L. Rutherford

ALTHOUGH considerable effort has been devoted toward the determination of the mechanical properties of pure metals, it is extremely difficult to compare the results of such work. This is because of differences in method and type of test, grain size, heat treatment, and purity of material. There is very little information on the properties of most of the high melting point reactive metals with purities greater than 99.9 pct. Previous evidence concerning the tensile properties of unalloyed metals show that: body-centered-cubic metals are brittle at low temperatures; face-centered-cubic metals remain ductile; some hexagonal metals remain ductile, others become brittle. It may be that traces of impurities decrease the low temperature ductility of the body-centered-cubic lattice. This would suppose that a body-centered-cubic lattice free from impurities would exhibit nearly the same ductility as a face-centered-cubic structure. The present investigation has been an evaluation of the tensile properties of zone refined iron in order to determine whether higher purity material than that previously evaluated behaves differently. Experimental Procedure In this investigation, high purity iron was zone purified using the floating zone method.' The starting stock was obtained from two sources. The first,

Jan 1, 1958

By R. F. Hollis, C. K. McArthur

PRIOR to the application of anion exchange, all recovery of uranium from acid leach liquors precipitated an impure product requiring further upgrading before it could be refined. The ion exchange process, on the other hand, provides excellent selectivity for extracting soluble uranium from leach liquors, so that high grade concentrates can be produced directly. The discovery that uranium is readily adsorbed by anion exchange resins, together with the experience of resin and equipment manufacturers in water treatment, led to rapid development of ion exchange in a multiple column operation. Many processing plants using fixed bed ion exchange are in operation or under construction in Africa, Australia, and Canada. There are a limited number in the U. S. Although the fixed bed process has been highly successful, the feed to the ion exchange columns must be a clear solution, which is obtained by filtration or by countercurrent decantation of leached pulps. With some ores, poor filtration or settling characteristics make production of a clear solution difficult. Most processing plants in the U. S. receive their ores from a number of small mines, and there is considerable variation in the settling and filtering behavior of the ores. An ion exchange process was therefore desirable in which the uranium could be recovered directly for the leached pulp by adding ion exchange resin, which could be then separated from the pulp by a screening operation. The process would thus resemble the cyanide-charcoal process in which gold is adsorbed from cyanide pulp by means of activated charcoal. Preliminary tests in which leached pulps were directly contacted with resin beads led to the development of the RIP process.

Jan 4, 1957

By A. H. Tousley

The cement industry is on the horns of an economic dilemma. Within the last ten years, its over- capacity in the United States has varied from 139- 127% of demand (Fig. 1). The most direct effect of this is seen in cement prices, which reached a peak in 1960, retreated steadily through 1966 and only recently climbed back to the 1960 level again. With prices in a slump and production costs estimated to be up almost 30%, there has been a steady drain on cement profits. Since 1960, labor costs have increased 86% while fuel costs have risen 18%. Meanwhile, customer service costs have also soared owing to the competition for cement customers and the wider variety of available cement products. This search for sales advantage has in turn led to a higher Blaine number, which means more grinding and hence bigger mills, more power, and, once again, higher costs. New plants as well as expansions and revisions to existing plants are also costing more owing to higher

Jan 1, 1971

By Chester O. Ensign

Results of the application of geologic knowledge to grade control have been remarkable. Grade reduction from dilution has been diminished from greater than 9% at the time of the program's beginning to about 2% at present. This has resulted in an increase of about 1.8 lb of copper per ton of ore mined and has made a substantial contribution to earnings at White Pine during the past two years. Even more improvement is expected in the future. The White Pine orebody, situated in the southwestern portion of the Keweenaw peninsula of upper Michigan, is a gently dipping stratiform or bedded deposit. Copper distribution is stratigraphically controlled with higher values being confined to specific beds in the ore column. Room-and-pillar mining is practiced. Mining technique and geologic characteristics present a special array of problems in controlling the grade of ore.

Jan 4, 1964

By G. R. Mansfield

THE third year of Government exploration for potash by the U. S. Geological Survey and the U. S. Bureau of Mines under the authorization of the act approved June 25, 1926 (Public 424-69th Cong.) is drawing to a close. The results thus far obtained are thought to be sufficiently interesting and satisfactory to justify the presentation of a brief pre¬liminary account of the work. REVIEW OF EARLIER EXPLORATION The general geologic similarity of the Permian basin of Texas and New Mexico to the potash field of Germany had long ago suggested the possibility of the presence of potash salts somewhere in that basin, but petroleum exploration was then making little headway there and the necessary data could not be obtained. The discovery by Udden in 1912 of potash in brine from the Spur well in Dickens County, Texas, was the first direct evidence of its presence. In 1915-17 the U. S. Geological Survey drilled a test well with standard tools at Cliffside near Amarillo, but failed to find potash. Nevertheless, an observer has been kept in the field, at first in cooperation with the Texas Bureau of Economic Geology but since 1922 by the Survey alone, to secure data and samples from oil and gas tests. Since the discovery of oil in Reagan County in 1923 exploration by drilling has been rapidly extended to many parts of western Texas and southeastern New Mexico. The identification of the potash-bearing mineral polyhalite was first announced by the Geological Survey in June, 1921, the material having come from cuttings from the Bryant well in Midland County and the Burns well in Dawson County, Texas. Successive discoveries and announcements of similar purport aroused widespread interest in potash exploration, which culminated in the action by Congress already noted.

Jan 1, 1929

By D. R. George, J. R. Ross, J. D. Prater

In the United States nearly 200,000 tons of copper per year are being produced, by leaching waste rock and oxidized copper ore with dilute sulfuric acid-ferric sulfate solutions and precipitating the copper on scrap iron. The flow of solutions is in excess of 80 million gpd. A survey conducted by the U.S. Bureau of Mines in late 1965 at 14 mines in Arizona, Utah and Nevada, showed that with a few exceptions, the solutions contain from two to a maximum of 15 ppm U3O8, and there is strong evidence that these represent equilibrium concentration and not merely an accumulated in-process inventory resulting from recycling the solutions for many years. Consequently, it is believed that uranium could be recovered at a constant rate as long as mining and leaching operations continue. Preliminary surveys and estimates by the USBM indicate a production potential of possibly 1000 tons of U3O8 per year at a cost of less than $8 per lb if the major process streams from most of the large copper mines in the western United States were to be treated. Laboratory research by the USBM showed that the uranium could be efficiently recovered as a specification-grade uranium concentrate by a combination of ion exchange resin and solvent extraction of liquid ion exchange techniques. A joint pilot plant investigation by Kennecott Copper Corp. and the USBM was conducted on solutions from the Bingham Canyon mine to evaluate a new system of countercurrent ion exchange developed during the laboratory studies. In subsequent small-scale continuous tests, recovery of uranium from the pregnant eluate by solvent extraction and chemical precipitation techniques was investigated.

Jan 1, 1968

By Edgar Stansfield

ONE of the most striking features of the coal series passing from peat through brown coal, lignite, etc., up to anthracite is the gradual reduction of moisture content with the increased coalification of the original plant material. Thus drained peat from a bog may contain 90 per cent water, brown coal contain 50 per cent, lignite 30 per cent, while a bituminous coal may contain only 1 per cent moisture. Moisture, therefore, is one of the important factors to be considered in coal classification, especially with the lower rank coals. With bituminous and higher rank coals the moisture content is less satisfactory for classification; it may even pass a minimum value and then increase with increasing rank to anthracite and superanthracite. Coal in an undisturbed seam contains moisture which is an integral part of the coal, but it may also be wet with free, underground water percolating through the seam. Only the former must be considered in evaluating the moisture content of the coal for classification purposes; this will be called the "true moisture" of the coal. When the seam is mined and sampled the sample taken may show the true moisture; on the contrary, it may contain in addition free mine water or, especially in dry, well ventilated mines, it may contain less than the true moisture. Coal contains unstable organic compounds which may decompose, with the production of moisture, when the coal is exposed to air at ordinary temperatures, or is heated with or without exposure to air. The potential moisture of a coal therefore is higher than its actual moisture. The lower the rank of the coal, the greater its instability, as a rule, and the greater the care necessary to avoid oxidation or decomposition in any investigation of moisture content. The majority of coal workers have preferred, on account of the difficulty in evaluating the true moisture of a coal, and for other reasons, to classify coals by analyses calculated to the dry-coal basis. A number of workers familiar with lower rank coals have recently insisted that the classification of such coals can be satisfactory only if analyses on the moist-coal basis are employed. The moisture-holding capacity of coal is therefore intimately connected with coal classification, and in this paper a procedure is outlined for determining the true moisture of a coal.

Jan 1, 1932

By John M. McAnerney

In 1955, the U.S. Army started to experiment in Greenland with tunneling in glacial ice and later in frozen glacial moraine. By 1960, long adits and experimental rooms had been successfully excavated. Full mechanization with coal-cutting machinery was most efficient in ice but drilling and blasting were necessary in bouldery moraine. In 1963, the U.S. Army Cold Regions Research and Engineering Laboratory, (USA CRREL; redesignated U.S. Army Terrestrial Sciences Center July 1, 1968) started a tunnel in the frozen silt of central Alaska near Fairbanks. The original adit of 360 ft (109 m) was successfully driven in the permafrost by a twin-rotor tunnel-boring machine, the Alkirk Cycle Miner. The workings were enlarged in 1966 and 1967 by standard mining techniques in which jackhammers, steam points, and augers were compared. A mechanical coal cutter was tried to supplement drilling and blasting. In 1968, airblasting techniques were used successfully for breaking out the frozen silt. All mine products were loaded mechanically and hauled by self-dumping shuttle car. Pneumatic methods of transport were tried for both dust removal and for conveying blast products up to 3-in. maximum size. Studies of the effects of natural winter ventilation through a shaft showed that tunnel closure could be reduced by lowering the adjacent ground temperature. It is concluded that underground openings in frozen ground should be cut and maintained at well below freezing temperatures to hold deformation to a minimum. HISTORICAL BACKGROUND This chapter deals with aspects of tunneling not previously discussed in the conference papers in this book. The chief differences are that the three tunnels lie entirely within frozen material and are relatively small, since they were constructed mainly for research. The primary objectives of the research were to develop underground shelters for military per-

Jan 1, 1970

By William J. Douglas, Jack T. Urie, Randall D. Metz

Production and financial planning for a new underground mine requires the coordination of equipment and coal reserves in a manner which assures that resources are utilized efficiently in achieving the target mine production. It is necessary to establish the productions which are attainable at the section level during different mining operations (advance, retreat, development) and under different mining conditions (roof, seam height, resource quality). It is also necessary to identify the interactions between production plans and ventilation equipment So that operations can be carried out without disruptions caused by inadequate ventilation. A set of computer models has been applied in planning a number of new coal, oil shale, and phosphate mines. A critical path production model, CPMINE, was used to determine face production levels for different cut sequences and seam heights, taking into account machine performance characteristics and operational availabilities under these varying conditions. The results formed a production data base for use in the mine sequencing model, MPLAN. This model processes each of the segments of a user-defined mine sequence network (strategy tree) taking into account the equipment available for mining operations and the previously determined production scheme devised by the mining engineer. Mine ventilation was analyzed with an expanded version of the Penn State MVS Ventilation model to determine fan and ventilation shaft requirements for supporting alternative production strategies. The MCOM mine cost analysis model has been applied to evaluate the economic performance of mining alternatives. The results of these studies were used to make decisions relating to equipment selection and acquisition schedules for both room-and-pillar and longwall mining systems. The approach and procedures which were used during these studies are described.

Jan 1, 1983

By K. H. Coats

This paper presents the development and solution of a mathematical model for aquifer water movement about bottom-water-drive reservoirs. Pressure gradients in the vertical direction due to router flow are taken into account. A vertical permeability equal to a fraction of the horizontal permeability is also included in the model. The solution is given in the form of a dimensionless pressure-drop quantity tabulated as a function of dimensionless time. This quantity can be used in given equations to compute reservoir pressure from a known water-influx rate, to predict water-influx rate (or cumulative amount) from a reservoir-pressure schedule or to predict gas reservoir pressure and pore-volume performance from a given gas-in-place schedule. The model is applied in example problems to gas-storage reservoirs, and the difference between reservoir performances predicted by the thick sand model of this paper and the horizontal, radial-flow model is shown to be appreciable. INTRODUCTION The calculation of aquifer water movement into or out of oil and gas reservoirs situated on aquifers is important in pressure maintenance studies, material-balance and well-flooding calculations. In gas storage operations, a knowledge of the water movemenr is especially important in predicting pressure and pore-volume behavior. Throughout this paper the term "pore volume" denotes volume occupied by the reservoir fluid, while the term "flow model" refers to the idealized or mathematical representation of water flow in the reservoir-aquifer system. The prediction of water movement requires selection of a flow model for the reservoir-aquifer system. A physically reasonable flow model treated in detail to date is the radial-flow model considered by van Everdingen and Hurst.1 In many cases the reservoir is situated on top of the aquifer with a continuous horizontal interface between reservoir fluid and aquifer water and with a significant depth of aquifer underlying the reservoir. In these cases, bottom-water drive will occur, and a three-dimensional model accounting for the pressure gradient and water flow in the vertical direction should be employed. This paper treats such a model in detail — from the description of the model through formulation of the governing partial differential equation to solution of the equation and preparation of tables giving dimensionless pressure drop as a function of dimensionless time. The model rigorously accounts for the practical case of a vertical permeability equal to some fraction of the horizontal permeability. The pressure-drop values can be used in given equations to predict reservoir pressure from a known water-influx rate or to predict water-influx rate (or cumulative amount) when the reservoir pressure is known. The inclusion of gravity in this analysis is actually trivial since gravity has virtually no efFect on the flow of a homogeneous, slightly compressible fluid in a fixed-boundary system subject to the boundary conditions imposed in this study. Thus, if the acceleration of gravity is set equal to zero in the following equations, the final result is unchanged. The pressure distribution is altered by inclusion of gravity in the analysis, but only by the time-constant hydrostatic head. The equations developed are applied in an example case study to predict the pressure and pore-volume behavior of a gas storage reservoir. The prediction of reservoir performance based on the bottom-water-drive model is shown to differ significantly from that based on van Everdingen and Hurst's horizontal-flow model. DESCRIPTION OF FLOW MODEL The edge-water-drive flow model treated by van Everdingen and Hurst1 is shown in Fig. la. The aquifer thickness b is small in relation to reservoir radius rb. water invades or recedes from the field at the latter's edges, and only horizontal radial flow is considered as shown in Fig. 1b. The bottom-water-drive reservoir-aquifer system treated herein is sketched in Fig. 2a and 2b. Here the aquifer

By E. A. Gulbransen, J. W. Hickman

INTRODUCTION DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may occur to such a degree that oxides may form in the body of the film and on the outer surface which are different from those that would normally form if the additional elements were not present. The use of transmisson electron diffraction may aid us in interpreting these phenomena. Up to the present time all of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physical state of the alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the removal of carbon by oxygen in a decarburization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with

Jan 1, 1948

By Dan G. Cojocariu, E. Ene-Danalache, I. Huber-Panu

A general model which represents not only batch but also continuous flotation in multi-cell machines is presented. This model considers both the size distribution and the distribution of flotabilities in a size class for valuable mineral particles in the pulp. The general expression is shown to reduce to several previously reported models. In addition, a number of new models are found to arise for different specific assumptions concerning the flotability distribution and/or the size distribution of the particles undergoing flotation. Several of these new models are tested experimentally using laboratory-scale batch and pilot-scale continuous data. Model parameters are estimated from this data and a comparison of calculated recoveries and those experimentally determined are presented. Finally, the influence of the feed rate, aeration rate and valuable mineral content of the feed on the recovery is examined.

Jan 1, 1976

By William Phillips

THE earliest mention of the sulphur deposits in what is now Culberson County, Texas, seems to be contained in "Explorations and Surveys for a Railroad Route from the Mississippi River to the Pacific Ocean, United States War Department, 1853-54." Captain John Pope (he was not commissioned Captain until 1856) had charge of one of the divisions of the Survey. In his report on the geology of the route, William P. Blake noted the analysis of a greenish earthy powder from the bed of Delaware Creek, at the springs, which contained 18.28 per cent. of free sulphur. The report states: "From the chemical examination of the waters of the spring, by Dr. Booth, it appears that chloride of sodium is the principal solid ingredient, but considerable quantities of sulphide of sodium are present. * * * * * The waters from the springs examined by Dr. Booth were alkaline, but it is possible that some of the springs are acid; and in this case the precipitation of sulphur would ensue on the mixture of the acid waters with those charged with alkaline sulphurets and the origin of the deposits of sulphur would he thus explained." This is the first reference to the existence of sulphur in that region, the first mention of the character of the water found there and the first suggestion as to the' origin of the deposits. The possibility of the existence of acid waters was confirmed by E. M. Skeats, nearly 50 years later.1 In this publication, Skeats says that the water from the sulphur deposits in Section 11, Block 114,, Township 5, contains 79.08 grains of free sulphuric acid per gallon. This locality is about 13 miles (21 km.) south of Delaware Creek and about 35-miles (56 km.) east of the Delaware Springs. The next published reference to the existence of sulphur in Trans-Pecos Texas is in the First. Annual Report of the Geological Survey of Texas, 1889, page 226, where W. H. von Streeruwitz mentions that sulphur is found in that region, but gives no further information. In the

Jan 9, 1917

By J. A. Church

I. Early Furnaces,......423 11. Experiments with the HIgh-Shaft FURnace,..... 426 III. ExperMents wIth the Wide FURnace,..429 IV. ExperEentS with Extreme BOSH,... 43.2 V. Survival of the 56 by 180 IN. Furnace,.434 VI. Recent ExpeEiments,.....436 VII. SUMMary,........438 I. Early Furnaces. Copper blast-furnace construction in America has long recognized a general standard in the rectangular water-jacketed shaft with separate forehearth. The details, however, and especially those relating to shaft dimensions, have had to meet a great variety of conditions, and show no uniformity whatever. Selecting a few of the present day Western plants, we find furnace lengths varying from 12.5 to 87 ft., widths at tuyere level from 42 to 84 in., and heights above tuyeres from 5 ft. 4 in. to 22 ft. 4 in.; and comparing present designs with those of the past, we meet contrasts no less striking. Unlike its transverse section, the length of a furnace has come to depend rather on the size of unit desired than on the requirements of smelting; and if the question of length be ignored, several of the various existing designs can be grouped together on the basis of a common transverse section. This section, having a width at tuyere level of 56 in. and a height above tuyeres of 18 ft., was developed at Great Falls, and the story of its development contains some interesting features. Ground was broken for the Great Falls works in the spring of 1891. About a year later, the concentrator was able to begin operation, followed within the next few months by the Brueckner, reverberatory, and converter departments, and in April, 1893, by the first blast fur-

Jan 1, 1914

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.' It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12'13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By V. B. Kurfman

The temperature, strain rate, and orientation deDendence of defbrnzation of single-crystal MgAg has been examined. The crystals exhibit a tendency to single glide and little or no hardening at 25°C for many orientations. A much higher hardening rate is observed when multiple glide occurs, such as can be initiated by surface defects. The tendency for easy glide becomes less dependent on surface preparation and orientation as T — 100°C and bars so tested often fail after one-dimensional necking-. At T > 200°C (transition temperature for single-crystal notch sensitivity and poly crystalline ductility) single glide diminishes and two-dirnensionul necking begins. The crystals do not strictly obey a critical resolved shear stress law, but show the influence of {loo) cracks in determining the slip mode. The results are correlated with the difficulty of sciperdzslocation intersection and semibrittle behavior of this compound in single-crystal and poly crystalline form. Comparisons are made with the slip selection mode observed in tungsten, with the reported observations of easy glide in bee metals. and with the mechanical behavior of poly crystalline MgAg. PREVIOUS work on tensile deformation of polycrys-talline MgAgl and bending deformation of single-crystal MgAg2 has shown that the compound is semi-brittle (i.e., notch and grain boundary brittle). If this semibrittleness is supposed to result from the difficulty of multiple glide (associated with the problems of superdislocation intersection) one might expect single crystals deformed in tension to show pronounced single glide and strong orientation dependence of hardening rate. These experiments were done to examine this supposition and to study the tensile deformation of a highly ordered system which may be considered bcc if the difference between the two kinds of atoms is ignored (actual structure: CsC1). EXPERIMENTAL Single-crystal ingots were grown by directional freezing as previously described.&apos; These ingots were sliced into a by a by 2 in, rectangular bars by electric discharge machining, then round tensile bars were conventionally machined to 1/8-in.-diam by 1-in.-long reduced section. The bars were typically tested without an anneal because of the problem of magnesium vapor loss and they were typically tested as mechanically polished. The analyses are within the same limits as those reported earlier; i.e., the average composition for each specimen is within 0.5 at. pct of stoichiometry, while the total range from end to end in a given specimen varies from 0.7 to 1.4 at, pct. There has been no indication in the results of any variation in slip or fracture mode attributable to the composition fluctuations. The slip systems were determined by two-surface analysis of the bars after testing to failure at room temperature. Single glide was so dominant that there was little difficulty in identification of the dominant slip system even though the tensile elongation to failure often approached 7 to 8 pct in room-tempera- ture tests. Elevated-temperature testing was done in a silicone oil bath and low-temperature testing was done in liquid Np or a dry-ice bath. All stress measurements are reported as engineering stress unless otherwise specified, and crosshead travel is used as the strain measurement. RESULTS The tendency toward single glide is best seen in the pictures, Figs. 1, 2, and 3, which depict deformation at fracture as a function of test temperature. While it is possible to find regions of secondary slip by careful microscopy, such regions are very small. The development of a ribbon-shaped configuration from an initially round section bar pulled at 100°C is typical, occurred by single glide, and illustrates the degree to which such glide continues. At temperatures =100°C the bars typically show elongation of 20 to 50 pct by predominently single glide. Despite the large elongation, fracture even at 150°C occurs in a brittle mode, Fig. 2, in the sense that it is an abrupt failure which shows no discernible necking in the second dimension of the bar&apos;s cross section (i.e., there is no appreciable action of any slip modes which would decrease the broad dimension of the cross section). Near 200°C the fracture mode changes slightly. Although most of the sample extension is by single glide, after the bar develops the characteristic ribbon shape it begins to neck in the second (i.e., broad) cross-sectional dimension. The bar becomes very thin in the "necked down" region, Fig. 3, and the reduction in area approaches 100 pct. Often there oc-

Jan 1, 1967

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.&apos; When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.&apos;4-&apos;7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By L. C. Morganroth

Magnesite both Massive and Crystalline MAGNESITES are. of two general classes-massive and crystalline. Massive magnesite occurs in serpentine, being formed by the breaking down or decay of serpentine-making minerals or rocks as olivine, etc. (All the magnesia contained by the olivine is not liberated, as a portion goes to make up the serpentine; the breaking up of this serpentine later forms more magnesite.) Serpentine in various stages of transformation is found in the vicinity of magnesite deposits. Massive magnesite is very widely distributed. It is found in Greece, . California, Africa, India, Australia, Mexico, South America, and deposits of varying sizes occur in several of the European countries. Those on the Island of Euboea, Greece, are probable the most important deposits of this character of magnesite. They have been worked for a number of years, the principal quarries or mines being 3 miles in the interior from the village of St. George. (St. George is on the west coast of the island, between the towns of Limni and Khalkis.) (Figs. 1 and 2). -The magnesite occurs in veins or lenses in serpentine. Some of these lenses are very large; one worked several years ago was approximately, 50 ft. in thickness, 75 to 100 ft. high and 300 ft. or more in length. The magnesite is pure white and makes a very prominent feature of the landscape. While massive magnesite is widely scattered over the world, many of the deposits are in veins too thin to work. The usual mode of occurrence is in the form of stock work, the deposits in Venezuela, Mexico, and many of those in California, being of this form. The veins vary in thickness from the thinness of paper up to several inches, running in all directions, occasionally leading to a mass or nucleus of some,size. The spaces between the veins are filled with a disintegrated serpentine in the form of sand. Several of the deposits in California would probably be workable, if they were more favorably situated with reference to transportation, but by far the majority of the deposits are too poor to work. At one deposit,

Jan 9, 1914