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By J. E. Hilliard

A procedure is described for determining, from measurements on a section, the moments of any degree n (i.e., the mean value of Dn, where D is a linear dimension) of the size distribution of particles (or grains) in an opaque sarnple. The analysis is applicable to particles of alnzost any shape and to any mixture of shapes. However, if absolute values of the wloments are required, it is necessary to know what shapes are present and the relative frequency of their occurrence. In addition, certain shape-dependent parameters have to be evaluated before the formulas can be used. The measurement required is the distribution of intercept lengths. This can be determined either visually or with an automatic scanning instrument. Corrections me derived for the bias due to instrumental end effects. The proposed analysis has the following advantages over existing ones: 1) Confidence limits are easily estimated for the measured properties or, conversely, the number of counts required to achieve a given accuracy can be determined. 2) The analysis is not restricted to particles of a special shape. 3) The error resulting from any known degree of departure of the actual from the assumed particle shape can be estimated. 4) The computations are simple and, apart from a change in constants, are independent of particle shape. 5) The number of particles per unit volume can be determined by a simple counting procedure. MANY procedures have been described for determining the size distribution of particles from measurements on a section (or plane of polish). They differ from one another in the property measured on the section (radius, intercept length, profile area) and in the method used for the numerical solution of the integral equation relating the property to the particle size distribution. However, all existing analyses share at least two of the following disadvantages. 1) They are limited to a particular shape of particle (usually spherical). 2) It is very difficult to determine how the statistical sampling error is propagated into the computed size distribution. The investigator thus has no means of knowing the reliability of his result and, what is of equal concern, he is unable to estimate how many measurements are required to obtain a result of the required accuracy. 3) It is also difficult to assess the error resulting from any deviation between the actual and assumed particle shape. The foregoing limitations stem from the complex relationship between the particle size distribution and the distribution of the property measured on the section. As will be shown, they can be avoided by defining the size distribution in terms of discrete parameters

Jan 1, 1969

By John B. Mertie

More than 200 minerals are known that contain the rare-earths and thorium. Monazite and bastnaesite, however, are the principal commercial sources of the rare-earths, and monazite is the principal source of thorium. Monazite was in demand in earlier years mainly for its content of thorium, which was used in the manufacture of Welsbach gas mantles; but beginning in the latter part of the nineteenth century, the rare-earths became progressively more important than thorium. Recently, however, the tenor of thorium in monazite has again become a matter of commercial interest. Rare-Earths and Thorium The rare-earths proper are defined by spectroscopists as the oxides of 14 elements with atomic numbers ranging from 58 to 71; but more commonly lanthanum, with an atomic number of 57, is also included, in which case these 15 elements are often designated as the lanthanides. Chemists also include scandium and yttrium as elements of the rare-earths. A second group of elements, beginning with actinium and including thorium, protactinium, uranium, and all the transuranium elements so far produced, with atomic numbers ranging from 89 upward, are chemically and structurally related to the lanthanides, and are known as the higher rare-earths or actinides. Berzelius discovered that the lanthanides could be separated roughly into three groups, based upon the solubility of their double salts, R2(SO4)3-K2SO4-2H2O, in excess of K2SO4. This separation, with the substitution of sodium for potassium, is still used commercially. The double salts of the cerium earths were found to be almost insoluble; the terbium earths, partly soluble; and the yttrium earths, completely soluble. Based upon the degree of solubility, scandium belongs with the cerium earths; and yttrium belongs with, and gives its name to, the yttrium earths. These three groups with their atomic numbers are shown below. [ ] The prevailing state of oxidation for the rare-earths is R2O3, but cerium may readily be oxidized to the tetravalent state, in which condition it may be separated chemically from the other cerium earths. Praseodymium and terbium may also exist with the valence IV, and samarium, europium, and ytterbium may have the valence II. Most of the elements of the rare-earths, however, are very difficult to separate, and their initial isolation required the work of many chemists over a period of 150 years.20 Fractional crystallization, fractional precipitation, and ion exchange are the principal methods so far used, and fractional precipitation is now employed commercially on a large scale. Ion exchange columns are

Jan 1, 1960

By E. L. Tucker

PREVIOUS investigations of E. L. Tucker and R. E. Head' related in particular to the effect of cyanogen compounds on galena, sphalerite, and pyrite, and their behavior in the presence of such com- pounds. The present contribution deals with the float- ability of the copper minerals and of pyrite. All experiments were performed on minus 200-mesh material, the method of preparation being the same as that described in the previous article. Flotation tests were made in a small mechanically agitated machine of 50-g. capacity designed in this laboratory by Gates and Jacobsen." General Naval Stores pine oil No. 5 and potassium xanthate were used in constant amount in all of the experiments; these agents were selected because of their present wide use in the flotation of copper minerals. Lime additions were varied to secure four 'final hydrogen ion concentrations, namely, neutral, 0.0005 per cent CaO, 0.003 per cent CaO, and 0.02 per cent CaO. The variation in lime addition was introduced to include the range of alkalinities employed in actual flotation practice.

Jan 1, 1926

By S. A. TAYLOR

THERE is probably no other mineral industry of which the public has as much information and misinformation as it has of the coal industry. Unfortunately, however, the general public's knowledge of the coal industry, outside of the particular kind of coal it is accustomed to, by reason of use, is largely made up of information received from newspaper and popular magazine articles, in which the mine workers are depicted as overworked and mistreated men, and the coal operators as "coal barons." Those who have any specific knowledge of exact conditions in the coal industry know how unjust and un- fair such an opinion of the coal industry is, not only to the miner but to the operator as well. Many reporters and writers of magazine articles are misled by statements regarding the condition of the miners that are exaggerated and not founded on facts and, if an investigation of the conditions of the miner's work, his habitation and surroundings were fairly made, it would at least compel more truthful statements by those who write for public reading. That such an investigation would not reveal anything that was wrong, or anything to be censured or cured, no one, I think, would maintain, but I do think that any fair investigation of the facts would show that conditions in and around the newer and later-developed coal mines and communities would compare favorably with those of manufacturing districts, and that where the mines and com- munities are old and not very attractive places to work, or live in, they carry with them other considerations, compensating for these conditions, and cannot be remedied by reason of a lack of sufficient coal to warrant economically any costly changes.

Jan 1, 1926

By T. D. Guldem, J. L. Kaae

ALLOYS with nominal composition of 45-Fe 35-Ni 20-Cr, ASTM-B-163, known under the commercial names of Incoloy 800 and Sanicro 31 (Alloy 800), are often employed at elevated temperatures for extended periods. Therefore, knowledge of the aging behavior of these alloys is of considerable importance. Significant decreases in ductility and increases in yield strength have been observed in the 45-Fe 35-Ni 20-Cr alloys containing about 0.4 pct Ti and 0.4 pct A1 after long-term aging at 540" to 700"~."~ However, no direct evidence has been presented for precipitation phenomena that might result in such changes. Strengthening effects have been attributed to the effects of local or-dering.3 Since y' precipitation (Ni3A1, Ti) is known to occur in similar alloys which contain more titanium and aluminum,4-7 it was decided to explore the possibility that y' might precipitate in these alloys and might be responsible for the changes in mechanical properties on aging. This note reports some observations of two distict types of matrix precipitates made by means of transmission electron microscopy, in a 45-Fe 35-Ni 20-Cr alloy containing 0.31 pct Ti and 0.4 pct Al. The steel used in this investigation was obtained from the Sand-vik Steel Works; it is designated Sanicro-31 (Alloy 800). The chemical composition of the alloy is given in Table I. Aging of solution-treated material at 700" and 800°C for 130 and 100 hr, respectively, produced the matrix precipitates shown in Figs. l(a) and l(b). It is apparent from these micrographs that the precipitate particles occurred in the form of thin square plates parallel to the matrix cube planes. Extraction replication and selected-area electron diffraction showed that the precipitates were M23C6. Coherency strains, consistent with the semicoherent nature of small M23C6 precipitates,' were evident for certain imaging conditions. In addition to matrix precipitation, preferential precipitation of M23C6 on dislocations was common, as has been reported previously for austenitic stainless steels.'" Specimens aged for longer times (-300 hr) at 700°C exhibited a different type of coherent matrix precipitate in addition to the M23C6. An example is shown in Figs. 2(a) and 2(b). In addition to the few large M23C6 precipitates, small precipitates exhibiting strain contrastl0,ll are present. The "line of no contrast" of the strain field of a given precipitate lies along differ-

Jan 1, 1970

By Howard C. Dunkle

Various factors can affect the quality of BIII2 and BIII3 steel as produced in a bessemer plant; among them: vessel-charging practice, blowing practice, ingot-pouring practice, ingot delivery-time practice, pit-heating practices, and ingot-rolling practice. Evaluation of the influence of ingot delivery time on quality has been chosen as the subject for this paper because this time is completely within the control of the operator, and on this particular factor there is a tremendous amount of information in the dusty archives of the average steel plant. In order to know how much improvement can be made and when attention should be directed to other factors that influence quality, in the continual struggle for improvement, the effect of ingot delivery time must be accurately evaluated. Once this is done, the importance of other variables can be accurately obtained, thus eliminating the necessity of resorting to opinions that are of doubtful value at best. In the study described herein, extensive use was made of the statistical card system as a method of determining the effect of ingot delivery time as a quality factor in bessemer screw-stock grades by simple direct correlation. The value of this statistical method as a means of accurately determining the influence of various factors has been amply demonstrated by Work1 for the bessemer process and by Hand and Gould2 and Fetters and Chipman3 for the open-hearth process. The quality records of 300,000 tons of bessemer screw-stock billets were used in this study of the effect of ingot delivery time on the rejections for breaks, pipe, check and seams. The reduction in the number of rejections for poor quality reduces the costs and increases the productivity per man-hour. The operator today, more than ever before, must know how to keep costs down, how to do it most quickly and in the best way, and how to obtain the highest quality in line with the ever increasing demands of the customer. It is necessary for him to know the individual relations and interrelations between various factors affecting the quality of the manufactured product if he is to produce material that will meet competitively the cost, performance, and quality demands of the trade. Significance of Steel Manganese, Mixer Silicon and Steel Sulphur as Quality Factors In order to obtain the highest grade of material it is necessary to control many factors—not just one or two, as operators

Jan 1, 1945

By P. Somasundaran

Flotation of minerals has usually been discussed in terms of solid-liquid interfacial phenomena. This paper discusses the relative importance of phenomena such as collector adsorption at other interfaces formed between the bubble, liquid and solid. Adsorption of collector ions of various chain lengths at liquid-gas and solid-gas interfaces has been obtained. The data have been analyzed under conditions corresponding to those of flotation to show the significant role of collector adsorbed on the bubble surface in determining the bubble-mineral attachment required for flotation, and consequently to suggest consideration of this role in the development of better flotation conditions. Vacuum flotation of quartz with alkyl ammonium acetate reported in the foregoing paper1 showed that the collector chain length has an effect on flotation even at concentrations below those necessary for hemi-micelle association of the hydrocarbon chains at a solid-liquid interface. This chain length effect might be explained by the following arguments: Hydrocarbon chains find it energetically favorable to be in a medium of low dielectric constant. Considering the possibility of an iceberg structure at the solid-liquid interface, such a structure would produce a region of lower dielectric constant at the solid-liquid interface than in the liquid phase, because the dielectric constant of ice is 2 to 3,2 while that of water is 80. Depending on chain length, this difference will certainly cause even individual ions to adsorb in higher quantities at the solid-liquid interface. Another mechanism to consider is the possible formation of dimers, trimers, etc and chain length would influence this formation. But, above all, the chain length effect on flotation at concentrations of low adsorption at the solid-liquid interface could be due to the significant but often-neglected role of the collector adsorption at the bub- ble surface. Collector ions or molecules are adsorbed both at the solid-liquid interface and the liquid-gas interface. Below the concentration for hemi-micelle association at the Stern plane adjacent to the surface, the bulk of the collector ions adsorbed at the solid-liquid interface are in the diffuse part of the double layer. If such systems, where there is a gas bubble coming in contact with the solid surface, are to achieve some degree of electroneutrality, those collector ions would have to migrate from the diffuse part of the double layer to the region directly adjacent to the surface during the induction period when the bubble is making contact with the solid. The time necessary for this migration would contribute to the induction period required for creation of the solid-gas interface. It seems reasonable that the induction period could be reduced sufficiently for flotation to occur if these collector ions were carried to the surface by the bubble. In an attempt to ascertain whether or not the bubble could possibly have sufficient collector ions at its surface to meet the requirement mentioned above, the adsorption density of the collector ions at the liquid-air interface was determined. For this purpose, the surface tension of alkyl ammonium acetate solutions was determined as a function of concentration. Adsorption densities of the collector at the liquid-gas interface were calculated using the Gibbs adsorption equation: where y is the interfacial tension and ri and pi are the adsorption density and the chemical potential, respectively, of the chemical species, i. Using the convention that the adsorption density of water at the interface is zero, the following relationship is obtained for the liquid-gas interface where lg refers to liquid-gas interface and RA+ refers to the alkyl ammonium ions. For dilute solutions, rf^-wri^&rfwW [3] where C is the concentration of the collector ions in solution. l?:: can now be evaluated using Eq. 3 and surface tension measurements.

Jan 1, 1969

By T. E. Ockershauser

The Southwest Antioch Oil Field located in T2&3N - R2&3W, Garvin County, Okla., was discovered in February, 1946, by The Globe Oil & Refining Co. and The Vickers Petroleum Co. at their Melinda Gibson No. 1. Oil production was encountered at a depth of 6,525 ft in 14 ft of lower Pennsyl-vanian sandstone. The producing sand, locally called the ."Gibson" or "Third Deese," is a sand bar deposit strung along the west flank of the Pauls Valley uplift in a northwest-southeast direction. The oil reservoir is defined to the east by the edge of sand deposition along the uplift and to the west by the gradation of sand into shale. Within the Antioch Unit, the sand dips from 150 to 400 ft per mile southwesterly and has a pay thickness varying from 10 to 55 ft and averaging 28 ft. Several areas of Gibson production have been developed, including the Katie pool on the south, the Elmore Area of the Southwest Antioch Gibson Sand pool. the Southwest Antioch Gibson Sand pool proper, the Southwest Maysville pool and the New Hope pool on the north. Production extends over a belt 22 miles long by about two miles wide and is continuous except into the Katie and New Hope pools. It appears that drilling will soon prove these intervening areas productive. To March 1, 1950, approximately 18,000 acres have been developed with 450 Gibson wells. It is likely this count will ultimately reach 32.000 acres with 800 wells. RESERVOIR The natural production of oil from the Gibson reservoir is primarily due to solution gas expansion though gravity also plays a part. There is no indication of water drive or evidence that an initial gas cap existed. Gibson oil has a stock tank gravity of 43" API and was saturated at the original reservoir pressure of 2.925 psi. It contained 1,3440 cu ft of gas per bbl in solution and had a high shrinkage of 70 per cent. Connate water amounts to 15 per cent. Reservoir temperature is 130°F. Porosity averages 15.5 per cent and permeability ranges from less than one md to over 1.000. Based on meacurement of 400 core plugs from 15 wells, 78 per cent of the permeabilities fell within the 10 to 1,000 md bracket and averaged l67. Primary oil recovery is estimated at 140 bbl per acre-ft or 22 million bbl for the present 137-tract unit. Due to unitization

Jan 1, 1951

By T. E. Ockershauser

The Southwest Antioch Oil Field located in T2&3N - R2&3W, Garvin County, Okla., was discovered in February, 1946, by The Globe Oil & Refining Co. and The Vickers Petroleum Co. at their Melinda Gibson No. 1. Oil production was encountered at a depth of 6,525 ft in 14 ft of lower Pennsyl-vanian sandstone. The producing sand, locally called the ."Gibson" or "Third Deese," is a sand bar deposit strung along the west flank of the Pauls Valley uplift in a northwest-southeast direction. The oil reservoir is defined to the east by the edge of sand deposition along the uplift and to the west by the gradation of sand into shale. Within the Antioch Unit, the sand dips from 150 to 400 ft per mile southwesterly and has a pay thickness varying from 10 to 55 ft and averaging 28 ft. Several areas of Gibson production have been developed, including the Katie pool on the south, the Elmore Area of the Southwest Antioch Gibson Sand pool. the Southwest Antioch Gibson Sand pool proper, the Southwest Maysville pool and the New Hope pool on the north. Production extends over a belt 22 miles long by about two miles wide and is continuous except into the Katie and New Hope pools. It appears that drilling will soon prove these intervening areas productive. To March 1, 1950, approximately 18,000 acres have been developed with 450 Gibson wells. It is likely this count will ultimately reach 32.000 acres with 800 wells. RESERVOIR The natural production of oil from the Gibson reservoir is primarily due to solution gas expansion though gravity also plays a part. There is no indication of water drive or evidence that an initial gas cap existed. Gibson oil has a stock tank gravity of 43" API and was saturated at the original reservoir pressure of 2.925 psi. It contained 1,3440 cu ft of gas per bbl in solution and had a high shrinkage of 70 per cent. Connate water amounts to 15 per cent. Reservoir temperature is 130°F. Porosity averages 15.5 per cent and permeability ranges from less than one md to over 1.000. Based on meacurement of 400 core plugs from 15 wells, 78 per cent of the permeabilities fell within the 10 to 1,000 md bracket and averaged l67. Primary oil recovery is estimated at 140 bbl per acre-ft or 22 million bbl for the present 137-tract unit. Due to unitization

Jan 1, 1951

By J. T. Peters, N. Schapiro, R. J. Gray

Petrographic studies of coal have resulted in a better understanding of the origin and composition of coal and have added to the knowledge of how and why coals differ in their response to various prepamtion and utilization processes. Petrographic methods can now be used in scientific economic exploitation of coals. Because the United States Steel Corp. is one of the largest consumers of coal and coke, there is a continuing interest in the corporation in perfecting a better understanding of coal so that it can be utilized more effectively. Coal is a heterogeneous substance composed principally of plant material that has been altered by a complex geochemical process to form rock. The science of coal is anthracology. The ultimate aim of anthracology is determining the relationships and differences among coals. The fundamental aim is finding out why coals differ. The practical application is determining how the differences in coals affect their utilization properties. Coal, like other sedimentary rocks, consists of more than one material. Fig. 1, a photograph of a natural fracture and a polished surface of a lump of coal, displays heterogeneity in terms of the banded ingredients present. The earliest attempts to describe coal were based on its hardness and appearance. ' Thus, coal has been described as hard or soft, bright or dull, and banded or nonbanded. The variations in the hardness and physical appearance of the coal reflect differences in materials that constitute the coal. The banded nature, lustre, and texture depend upon the relative proportions of the various constituent materials. Even the earliest petrographic investigations of coal produced evidence of of the heterogeneity of the coal substance and shoul have destroyed the concept of the unit coal molecule. Coals (Fig. 2) that appear the same frequently consist of different microscopic materials and may behave differently during mining, pulverization, washing, or coking. In Fig. 3, the upper photograph shows a bright at-trital medium-volatile coal, and the micrograph at the right shows some of the materials that constitute the coal. The lower photograph shows a bright attrital low-volatile coal and the corresponding micrograph shows material of similar origin to those from the medium-volatile coal. Any petrographic description of a coal that has meaning in terms of its utilization begins with a microscopic examination. Numerous attempts have been made to describe coal on the basis of the materials that constitute the coal.2*3 Initial petrographic studies were directed towards the question of the origin of coals without any true basis for studying the metamorphic changes in the

Jan 1, 1962

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960

By E. M. Cox, T. Rosenqvist

IN a recent investigation, carried out at the Institute for the Study of Metals, the affinity of sul-phur for iron, copper, and manganese was studied over the temperature range 700" to 1300°C.' It was found that copper exhibits a rather high affinity for sulphur, especially at higher temperatures; and attention was called to the possibility that copper when present together with sulphur in liquid steel would tend to lower the chemical activity of sulphur and thus interfere with the desulphurization process. It was clear, however, that the data for the equilibrium between pure copper and pure copper sulphide (Cu2S) could not give any quantitative information about the effect of copper when dissolved in liquid steel. The present work is concerned with the activity of sulphur in the diluted range of the binary iron-sulphur system, and with the influence of small amounts of copper on this sulphur activity. This investigation is in principle based on the same method previously described for the binary metal-sulphur studies;1,2 namely, reaction with hydrogen to form hydrogen sulphide. The equilibrium ratio PH2s/Ph2 in the equilibrium gas mixture is, for a given temperature, directly proportional to the sulphur activity. The activity of sulphur in liquid iron has previously been studied by Chipman and Ta Li,3 White and Skelly,4 and recently by Sherman, Elvander, and Chipman.5 Morris and Williams6 have studied the effect of added silicon, and Kitchener, Bockris and Liberman,7 and recently Morris and Buehl,8 the effect of added carbon on the sulphur activity. In present day steelmaking processes the steel bath contains between 0.01 and 0.1 pct sulphur, and the copper content may be as high as 0.5 pct. The equi-librium gas ratio (H2S/H2) would, for such a low-sulphur content, be too low to be measured with the experimental technique we use. It has been shown by previous investigators that the H2S/H2 ratio is closely proportional to the sulphur content up to about 1 pct sulphur. The sulphur activity at very low-sulphur content can therefore be calculated by linear interpolation between 0 and 1 pct sulphur. In order to show the general trend with increasing sulphur content, the present work has been carried out to about 3.5 pct sulphur. As the effect of copper was assumed to be more a function of the Cu/S ratio than of the absolute copper content, the runs with copper were made for certain constant values for this ratio.

Jan 1, 1951

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By J. B. Cheatham

Applications of the mathematical theory of plasticity promises to lead to the solution of many drilling and rock mechanics problems. ,Because of mathematical considerations, the inelastic behavior of rock has frequently been represented by a perfectly plastic model in conjunction with a yield criteria of the Coulomb or Mohr type. The totality of all stress states for which a solid ceases to behave elastically can be represented as a limit surface in stress space. ,Probing of such limit surfaces indicates details of strain hardening which are not provided by the standard triaxial testing procedure. Probing tests of the limit surfaces have been performed on Cardova Cream limestone to provide data for extending plasticity theory to cover situations in which consolidation and strain hardening are present. Test results indicate that this highly porous limestone undergoes a permanent volume decrease when it is subjected to hydrostatic pressures in excess of 3,500 psi. A virgin sample tested under a confining pressure of 1,500 psi has a yield strength of 1,700 psi; however, if the sample is subjected to a consolidation pressure of 5,000 psi, before testing at 1,500 psi, the yield strength is raised to 2,300 psi. Thus, both consolidation and strain hardening are important considerations in describing the mechanical behavior of this limestone. Tests conducted with the axis of the core having different orientations indicate that this rock is also anisotropic. Portions of the initial and subsequent limit surfaces are determined for samples loaded either perpendicular or parallel to the bedding planes. INTRODUCTION Previous experimental work in rock mechanics indicates that no mathematically tractable constitutive theory is inclusive enough to describe the mechanical behavior exhibited by all types of rocks under all conditions of stress and temperature. Indeed, the type of deformation encountered in a single type of rock is known to depend upon the stress and temperature conditions in the rock during deformation.l-5 Certain rocks and minerals, notably those minerals composed of ionic salts, have been shown to exhibit plastic deformation when tested under conditions of high confining pressure.2 Since the mathematical theory of plasticity provides simplifications over the theory of elasticity in certain types of problems, such as those in which limit analysis can be applied, it is of interest to know under what conditions plasticity theory may be applied to rock mechanics problems. The following factors determine the nature of the deformation a particular specimen will undergo: (1) the microscopic structure of the rock, i.e., the structure visible under an optical microscope, including number of phases, porosity, distribution of phases, (2) the mineralogical structure of the solid phases, (3) the conditions of stress and the rate of change of stress and (4) the temperature. Extensive experiments on Yule marble, Carthage marble, Solenhofen limestone and other calcerous rocks indicate that these relatively nonporous rocks deform plastically under certain conditions of loading, and creep under other conditions of loading.l-3 This study is concerned with the behavior of Cordova Cream limestone (Austin chalk) which is also composed almost entirely of calcite and thus has the same mineralogical composition but, because of a rather large porosity, it possesses a different microscopic structure. This investigation was undertaken to learn if Cordova Cream limestone deforms plastically despite the embrittling effect of the pore spaces, and to provide data which can be used to determine whether the mathematical theory of plasticity can describe the mechanical behavior of Cordova Cream limestone. A brief discussion is given of some of the underlying principles of plasticity theory concerning stress space and limit surfaces. Strain hardening is defined and a discussion is given of how the mechanical behavior of a material can depend on the previous history of the loading. This is followed by a description of the experimental procedures

By Albert C. Harding

FOR several years barite (BaSO4) production has topped such better known minerals as feldspar and fluorspar in annual tonnage and is now well established among our foremost nonmetallic industries. DESCRIPTION Of widespread occurrence in the United States, barite is relatively soft (hardness, 2.5 to 3.5), inert, heavy (specific gravity, 4.5), and is also called "barytes" (sometimes pronounced "bear-i-tease"), "heavy spar" and "tiff." It occurs with granular and earthy structure but usually has coarse, orthorhombic crystallization. It is commonly white, and although occurring in various shades of red, yellow, and gray, barite always gives a white streak and can be scratched by the ordinary prospecting pick. Its softness and weight are usually sufficient to establish field identification. Another aid is the "rotten egg" odor of H2S which sometimes emanates from freshly fractured surfaces. Barite can be readily distinguished from two other minerals which have somewhat similar occurrences and characteristics. The relatively rare celestite, strontium sulphate, has a specific gravity slightly less than 4.00 and gives a distinctively crimson color in a flame test. The very rare witherite, barium carbonate, has a specific gravity of 4.3 but readily effervesces with dilute hydrochloric acid. OCCURRENCE All known commercially important barite deposits in the United States occur as re placements or cavity fillings in schists, shales, limestones, dolomites, and quartzites, or as residual deposits from such formations. In Georgia, Tennessee, North Carolina, and Missouri, high-grade barite is recovered as fragments from residual clays covering quartzites and dolomites. In Arkansas, Nevada, and California, barite, usually of lower grade, is mined from replacement deposits. These seven states contributed the entire production reported by the U. S. Bureau of Mines for 1945 as given in Table I. [TABLE 1-Crude Barite Sold or Used by Producers in 1945 STATE SHORT TONS Arkansas260,660 Missouri225,467 Georgia110,393 Tennessee32,812 Nevada28,919 Other States37,811 Total 696,062] "Other States" included only California and North Carolina. Such a large part of this undistributed production came from California that that state probably outranked both Nevada and Tennessee. For the second consecutive year Arkansas was the leading producing state, particularly worthy of note because there was no commercial production of barite there prior to 1941 and because the entire production of Arkansas has come from one large deposit which is being operated by two companies. CONSUMPTION [The 1945 consumption as reported by the Bureau of Mines was: 482,442 tons as ground barite 139,288 tons in making lithopone 99,173 tons in producing barium -- chemicals Total 720,903 tons]

Jan 1, 1947

By HORACE V. WlNCHELL

Location. THE St. Helens mining-district, indicated in sketch-map, Fig. 1, is chiefly in Townships 9 and 10 North, Ranges 5 and 6 East, of the Willamette meridian, in Skamania county, Wash. There is no railroad or even a wagon-road at present connecting it with any base of supplies; access is usually by wagon-road for FIG. I.-SKETCH-MAP OF THE STATE OF WASHINGTON. about 50 miles from the town of Castle Rock to Spirit lake, and from that point by pony-trail from 6 to 10 miles farther. History. Nearly 20 years ago two German farmers, totally inexperienced in prospecting, penetrated this region upon a hunting and fishing-trip. Their attention was drawn to numerous joints and crevices filled with black, glistening tourmaline, and con-

Oct 1, 1912

By A. A. Berk

LAGGING technology and the slow spread of information have been the chief obstacles to widespread participation in minimizing the industrial pollution load. These obstacles can be conquered by fact finding and applied research. There are three aspects to the problem of water-borne mineral waste: to minimize the amount being thrown away, to select a predisposal treatment, and to use the products or dispose of them. It is often possible to minimize the waste by making very minor changes in the process that produces it. For example, a manufacturer of automobile bumpers greatly reduced the dragout 'from a plating bath by modifying the design and position of two boltholes.' A plater of automobile hubcaps installed a drainage bar and decreased the loss of chrome-plating solution to the rinse water by about 80 pct.' The mill at a western mine found it possible to discard 60 to 70 pct of an ore with minimum treatment," so that the processing effort could be concentrated on a high-graded slime, with significant reduction in costs and improvement in recovery. The possibilities for waste reduction through process changes are limited only by the imagination. A recent patent points out the advantages of using No. 1 fuel oil instead of water in wet-process cement making;& the fuel oil presumably has better properties than water for this purpose and is said to be almost com'pletely recovered or utilized, so that there is no waterborne waste. Recycling to reduce wastes and improve process economy is very well illustrated in vanadium and uranium recoveries from relatively low grade ore. Ores containing 6 pct calcium carbonate were found to give poor vanadium recovery by the salt-roasting process because the vanadium was converted to water-insoluble calcium vanadate. Following the salt-roasting process, sulfuric acid was used to leach the uranium. Enough calcium sulfate was formed

Jan 1, 1958

By S. W. Kennedy, M. Cohen, L. D. Calvert

A high-temperature X-ray diffraction method has been used to study the composition and the kinetics of formation of oxide scales at 800 °C on iron and pure iron-nickel alloys containing 25.6, 75, and 84 pct Ni. This technique has been combined with chemical analysis, and metallographic examination, and determination of weight-gain time curves. The 75 and 84 pct Ni alloys form a three-layer scale consisting of porous NiO next to the metal, a spinel layer, and a -Fe203 on the outside. The 25 pct Ni alloy produces a scale of spinel and Fe,O,, in which, however, traces of FeO and NiO are observed near to the metal. On all the nickel alloys the Fe20, is orieqted with the (107) plane parallel to the surfaces. The exposed surface of the Fe20, is in the form of needles whose axis is perpendicular to the specimen surface. Although the alloys show nonuniform oxidation rates as determined from weight-gain measurements, the X-ray data indicate that the total scale and individml scale layers grow uniformly and parabolically. Deep subscale formation is observed in the 25 pct Ni alloy only. This appeared to be associated with cracking of the scale and penetration of the oxygen along the grain boundaries. ALTHOUGH film formation has been investigated by high-temperature electron-diffraction techniques, for example by Gulbransenl and Hickman,' there have apparently been no investigations of scaling by methods permitting study of the scale during formation at the reaction temperature. Methods involving quenching of scales are based on the working assumption that no significant changes take place on cooling. In general, however, compounds may disproportionate, and the different thermal expansions of constituents may cause disruption of the scale on cooling. In particular, some scales cannot be quenched without spalling. These difficulties are avoided by X-ray diffraction examination at the temperature of formation. High-temperature diffraction procedures also provide a method of determining the kinetics of formation of each phase separately in a multicom-ponent scale. The scaling of binary iron-nickel alloys Containing up to 30 pct Ni at a temperature of 800°C has been studied by Benard and Moreau using cooled specimen~,~ whilst Foley, Druck, and Fryxel14 made an electron-diffraction study of cooled oxide films formed on an iron 42 pci Ni alloy. In the present work the scaling of three iron-nickel alloys containing 25.6, 75, and 84 pct by weight of nickel, at 800°C in oxygen at atmospheric pressure was investigated by X-ray diffraction techniques using a Norelco Geiger-counter diffrac-tometer. The oxidation of iron was investigated for comparison. In addition normal metallographic examinations and chemical and X-ray analyses were made, and weight-gain time curves obtained. EXPERIMENTAL Materials Used—The analyses of the alloys were as follows: Percent by Weight Nickel 25.6 pct 75.4 pct 83.2 pct Aluminum 0.004 None found 0.002 Cobalt — 0.05 0.05 Chromium — — — Silicon — 0.01 None found Carbon All less than 0.05 pct The chemical analysis of the iron was: Al— 0.002 i 0.001 pct, C—0.007 pct, Cr less than 0.001 pct, Cu—0.002 ± 0.001 pct, Mn—0.003 ± 0.001 pct, N—0.0002 pct, 0-0.013 pct, P—less than 0.0002 pct, Pb—not detected, S—0.0017 pct, Si—0.0095 pct, Sn—none detected. This iron was the same as that used to make the alloys and was obtained from the same source-Vacuum Metals Corp. One specimen of pure iron from The British Iron and Steel Research Association was used for preliminary investigation. Specimens were machined to shape from cast rod, polished (the final polish being with 600 Sic paper), degreased in trichlorethylene, washed, and etched. The etching and neutralizing procedure adopted by

Jan 1, 1960

By T. S. Spice, H. L. Lovell, R. W. Utley

With the increased demand for lightweight aggregate, such materials have been manufactured from slags, clays, slates and, to a minor extent, the refuse of coal preparation processes. The latter source is attractive due to current interest in eliminating air pollution and improving the unsightly appearance of refuse piles as well as potential economic advantages, if a satisfactory product can be manufactured. A study has been made relating the composition of coal refuse, expressed as washability data, and the properties of a resulting aggregate. Three different refuse samples (bituminous and anthracite) were separated at gravities ranging from 1.4 to 2.96. Their chemical composition was determined. Aggregates were prepared in the laboratory from these fractions before and after ashing, at temperatures between 1250' and 1350°C. The specific gravity, expansion and compressive strength of the products were measured. The response of the refuse to bloat is related to the chemical composition of the ash to yield a glass of desirable viscosity and to the presence of a material which will form a gas in the appropriate temperature range. Carbonaceous material within the particle is a negative factor since after the glassy phase forms, oxygen cannot enter the mass thus inhibiting bloating. Precombustion of the refuse is also detrimental since it removes substances of gas-forming capability. The fraction sinking at 2.60 yielded an aggregate which had the lowest specific gravity, greatest expansion and greatest compressive strength. The purpose of this study was to seek and evaluate possible relationships between the composition of coal refuse, as expressed by washability data and factors affecting the production of a lightweight aggregate from refuse by bloating. The study was related to an intense program in the Department of Mineral Preparation at the Pennsyl- vania State University to study the possible elimination of air pollution from coal refuse fires by producing a low-carbon secondary refuse. Another phase of this program is considering possible uses of such a secondary refuse. Thus one study was to determine if a lightweight aggregate could be produced from this new refuse material and what effect the nature of refuse beneficiation would have upon the characteristics of a commercial aggregate product. It was hoped that these studies would assist in the design of a process and in establishing the optimum specific gravities at which refuse separation could be made in respect to the production of a low grade fuel from the float product and a raw material for lightweight aggregate from the sink product. The combination of producing a saleable low grade fuel and a lightweight aggregate, while at the same time minimizing disposal costs and air pollution contributions would be attractive to the coal mining industry. MECHANISM OF BLOATING Austin, Nunes and Sullivan,1 Ehlers,3 Everhart, 4 Riley7 and others, have stated that bloating is an expansion process in which two essential conditions exist simultaneously. These are: the development of a glassy phase over a relatively wide temperature range (the viscosity of this glassy phase plays a major role in the retention of the evolved gases) and the evolution of gases (SO2, SO3, CO2 and O2) from mineral decomposition in sufficient quantities at appropriate temperatures to form a cellular structure in the mass. Unless these two "type" reactions take place at the same time or in overlapping ranges of time and temperature, cellulation will not occur. In this event, the gas will escape or the melt will be too fluid to retain it; or if retained, the cells may be too large or the walls too thin for good strength in the product. The stages that occur when clays and shales are heated in an oxidizing atmosphere may be summarized as follows: 1) Drying and removal of free water to 200°C. 2) Absorbed water dehydration period (200 to 480°C). 3) Chemically-combined water dehydration period (480 to 700°C).

Jan 1, 1965

By R. Ingerson

Bore surfaces of used guns commonly show a pattern of cracks in various degrees of development. It has been suggested that these cracks may aid erosion by providing channelways for the gases, eventually leading to the tearing out of blocks of metal. Under the general studies of gun erosion conducted at the Geophysical Laboratory it appeared desirable to consider this factor, and to determine the resistance to surface cracking offered by gun steel and by various other materials that might be used in the bores of guns. Method and Apparatus In order to make such a determination it is necessary to have (I) an arrangement in which the surface to be studied can be subjected to conditions similar to those in a gun with respect to temperature, pressure (developed by explosion gases), composition of the gases and length of time the surface is exposed to the gases; and (2) a specimen that can be examined readily after any number of shots, and then fired again, if necessary. The first of these conditions can be met by using an explosion vessel designed by H. S. Roberts of the Geophysical Laboratory. Fig I shows a cross-section of the apparatus. The "gun" G from which the charge is fired is made from the receiver of a caliber 0.30 army rifle, M1903, and the charges are prepared in caliber 0.30 cartridge cases. The test specimen S is held in place by a cone-shaped plug P and by a steel bridge B which is bolted to the outside of the explosion vessel on either side of the section shown. The plug, in turn, is held in place by a screw collar C. Maximum pressure is controlled by a brass rupture disk R. Part of the explosion gases flow past the two flat areas on S. Temperature and composition of gases, and the time before the rupture disk breaks, can be controlled by amount and kind of powder used, and pressure can be controlled by using rupture disks of different thickness. While the explosion vessel used was not designed so that temperature and pressure could be measured, in other vessels of closely similar size and shape containing proportionate charges of the same kind of powder as that used for standard testing procedure, values of 2700°K and 50,000 psi were obtained. Since the orifices past the flat areas on the plug are small compared to the rupture disk hole (I:I6), most of the gas goes out through the rupture disk when it breaks. The amount that goes by the plug depends on (I) the pressure attained before the rupture disk breaks and (2) the time it takes for this pressure to be built UP. The second condition (examination at will after any firing) is met by using for specimens short rods that have flat areas ground on opposite sides. These flat

Jan 1, 1949