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By W. D. Potter, E. T. Peters

Single-crystal films of boron have been prepared by thermal reduction of purified BCl3 with subsequent deposition of boron onto oriented silicon substrates. The structural properties of films prepared under various experimental conditions have been determined by light microscopy and "grazing-" angle electron-diffraction analysis. An orientation relationship is proposed for silicon and a-rhombo-heclral boron which can be described as: (111)Si (112)B; [110]Si [110]B ElEMENTAL boron is known to have a high energy gap* and consequently has potential value as a high- *Energy gaps of 1.35 to 1.55 ev1-3 and 2.0 ev4 are reported for ß-rhombohedra1 and a-rhombohedra1 boron, respectively. temperature semiconductor.5 Exploitation of this property, however, has been hampered by the unavailability of pure, single-crystal boron. Two recent symposia6,7 have treated the subjects of purification, crystallization, crystal structure, and properties of boron and provide a foundation for further investigation in these areas. The structure, lattice constants, and observed ranges of stability for four reported polymorphs of boron8°12 are listed in Table I. The rhombohedral structures are generally accepted as true polymorphs whereas the tetragonal structures are believed to be transient. Most currently available single crystals of boron are grown by Czochralski and floating-zone methods. Unfortunately, these crystals generally contain numerous defects and are highly strained as a result of the polymorphic transformations and thermal contractions which accompany cooling. Recently, Armington, Potter, and Tanner13 have reported the formation of single-crystal films of boron on silicon single-crystal substrates through thermal reduction of BC13 by hydrogen. Boron E. T. PETERS, Junior Member AIME, is Senior Scientist, ManLabs, Inc., Cambridge, Mass., and W. D. POTTER is Research Chemist, Air Force Cambridge Research Loboratories, L. G. Hanscom Field, Bedford, Mass. formed at temperatures near 1000°C was identified as the a-rhombohedra1 form, consistent with expectation. The present paper describes a continuation of this work with specific reference to characterization of the structural features of the deposited boron films. The ultimate goal of this program is to produce large-area single-crystal films of a-rhombohedra1 boron to be used for electrical and optical studies by other workers. PREPARATION OF BORON FILMS The experimental procedure of preparing thin films is similar to that described by Theuerer14 for the epitaxial growth of silicon by thermal reduction of SiC14 and has already been described as applied to the preparation of boron thin films.13 Briefly, a mixture of BCl3 vapor and dry hydrogen is passed over a heated silicon substrate. Thermal reduction of the BC13 allows deposition of boron on the substrate. The substrates were {111}-oriented, single-crystal silicon. Square specimens 0.63 cm on an edge by 0.1 to 3.0 mm thickness were prepared by

Jan 1, 1965

By G. S. Scott, G. W. Jones

ECONOMIC waste caused by mine fires may become considerable,15 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters-such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control. necessarily must be based upon one or the other, or both, of these two principles. . The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion) ; and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. OXIDATION OF COAL Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored.6,16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By G. B. Craig, G. L. Montgomery

A simple technique has been developed which reveals glide dislocations in zone-refined aluminum as etch pits. The technique has been tested quantitatively by making dislocation counts on aluminum single crystals deformed in pure bending. The method has the advantage of being insensitive to the orientation of the surface under examination. A number of etchants which will reveal dislocations in annealed aluminum have been reported.'-' These etchants apparently depend on decoration of the dislocations by an impurity (probably iron) and cannot, therefore, be used to reveal fresh glide dislocations. In addition, it is unlikely that screw dislocations will be etched because of their small attraction for impurity atoms. Amelinckx6 has reported that glide dislocations located along slip traces can be revealed by fluo-rated aqua regia. This work indicated that dislocations themselves, irrespective of decoration by impurity atoms, are responsible for the etch pits. However, as a result of additional etching experiments, Wyon and Marchin7 concluded that dislocations alone are not sufficient to explain the localization of etch pits on slip lines in aluminum using chemical etch-pitting techniques. In addition, their results show that glide dislocations are revealed only on surfaces approximately parallel to a (100) axis and that not all slip systems are attacked. These observations have been confirmed by the present authors. The technique described in this article is insensitive to the orientation of the surface, and reveals dislocations on all glide systems. Fig. 1 shows a deformed region in the neighborhood of a scratch. Dislocations can be seen along three slip traces. In the present work, single crystals of zone-refined aluminum are polished for from 2 to 5 min in a chemical polishing reagent held at 100°C, as described by Herenguel and second:' H2Sol 60 pct H3PO4 30 pct HNO3 10 pet The samples are then coated with a thin oxide film by annealing in air at 450°C for 1 hr and cooling in the furnace. After deformation, dislocation etch pits are developed by immersing the specimen in the same polishing solution which is now held at a temperature of 50°C. The formation of small hydrogen bubbles indicates that etching has occurred. The sample is immediately removed from the solution. Prolonged etching results in enlargement of the pits and, in regions of high dislocation density, the overlapping and loss of resolution of individual pits. It is the experience of the authors that contact with iron will ruinously contaminate the reagent. With careful etching, dislocations separated by half a micron can be resolved optically and the method has been shown to be sufficiently sensitive to reveal dislocations produced during the pre-easy glide region of deformation, Fig. 2. A few examples of glide-dislocation configurations, as revealed by this technique, are shown in Figs. 1 to 4.

Jan 1, 1964

By Nelson Severinghaus

Mineral fillers have been defined as inert materials that are included in a composition for some useful purpose. Because this definition and the scope of this review are not specific-indeed, exceptions abound-accurate total statistics are unavailable. One source estimates the total production in the United States in 1979 at 11.3 Mt (12.5 million st) valued at $534 million, averaging $49.19 per ton. Included are a broad group of minerals-asbestos, barite, bentonite, ground limestone and dolomite, clays, diatomite, feldspar, micas, silica, talc. Additional references will be made to synthetic mineral-derived fillers such as aluminum hydrate, precipitated calcium carbonate, and pyrogenic and precipitated silicas and silicates. A section on related uses at the end of this chapter covers absorbents and filters. Mineral fillers can be included in compounds to accomplish a variety of final results. Hardness, brittleness, impact strength, compressive strength, softening point, fire resistance, surface texture, electrical conductivity, and a host of other physical characteristics may be modified by the inclusion of fillers. These effects are the result of properties of the fillers, including chemical activity, hardness, particle size, shape and distribution, surface structure, color, density, and refractive index. To facilitate an overview of the mineral filler industry, this chapter will review the general usage of fillers, the inherent characteristics that intensify their utilization, and similarly their manufactured characteristics. Major using industries will then be examined in detail. Specific information on deposits and processing for industrial minerals will be found in the appropriate commodity chapter. All of these same minerals have additional significant uses based on their chemical composition or other characteristics. References will be found in other use chapters and summarized in commodity chapters. The chart in Table 1, updated from the 4th edition of Industrial Minerals and Rocks, illustrates the major mineral fillers (both natural and manufactured) and their more important end uses. Use of Mineral Fillers Archaeologists have found that more than 5000 years ago, bitumen used for mortar and waterproofing contained mineral contaminants that acted as fillers. Since that time man has added mineral products to compounds to improve certain characteristics. Perhaps the most common objective of filler usage is reduction of cost of the end product. Certainly the inclusion of a filler that costs 2¢ per 0.45 kg (lb) will reduce the cost of a plastic product whose resin costs 50¢ per 0.45 kg (lb). But the decision to use a specific filler is not that simple. It may "soak up" binder, making a compound more viscous and perhaps preventing its flow into a mold as an injection molding compound, but similarly will give good anti-sag characteristics to putty, caulking compound, or undercoating. Fillers may be incorporated to modify: 1) Cost 2) Physical characteristics 3) Flow characteristics 4) Fire resistance 5) Density 6) Heat conductivity 7) Color or brightness and opacity 8) Hardness, brittleness, impact strength 9) Deformity, viscosity, softening point 10) Processing problems 11) Electrical conductivity 12) Surface texture 13) Thermal expansion characteristics 14) Abrasion resistance

Jan 1, 1983

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By Leendert de Witte

A review is given of the principles on which recently proposed methods of electric log interpretation in shaly sands are based and of the evidence brought up in support of the theoretical derivations. It is. pointed out that the qualitative techniques suggested to date have a tendency to be too pessimistic in the prediction of the presence of commercial hydrocarbon accumulations. In the quantitative treatment, a new concept is introduced, namely that of strongly reduced activity of the double layer counter ions which are present near the negatively charged rock surfaces. This lemmu when applied to the calculation of the equilibrium concentratiotls of interstitial waters yields a set of very simple relations. The resulting expressions for electrochemical potentials across rock samples appear in satisfactory agreement with laboratory experiments. The formulae obtained for the electrical conductivity of shaly formatioris are of the same form as those arrived at empirirally by previous workers. Combination of the expres.riorls for potentia1s and conductivities gives a direct proof of the Tixier relation which states that for shaly water sands the product of apparent formation water resistivity and apparent formation factor equals the resistivity of the sand 100 per cent .saturated with formalion water and which was verified by the work of Wyllie and Perkins and their co-workers. The relations for the resistivities and spontaneous porer11inI.s have been extended to the case of hydrocarbon hearing shaly formations, thus laying a formal basis for the quantitative interpretation of electric logs in shaly oil sands. INTRODUCTION The presence of disseminated clays in porous rocks saturated with electrolytic solutions has a strong influence on the transference of ions taking place under electrical or chemical potential gradients. Both the electrochemical emf's in evidence on the SP curves of electric logs and the electrical conductivity measured on resistivity logs arc directly dependent on the ionic transference in the interstitial waters of the formations traversed by boreholes. A large number of researches have been carried out on the nature and magnitude of the effects of clays on ionic transference. The most recent of these have been described in papers by McCardell and Winsauer,1 2 Wyllie and Southwick,3 poupon, Loy, and Tixier,4 and by Perkins et al.5 Most of these authors consider the effects of the clays as due to the fixed negative charges on the clay lattice. These charges cause the formation of diffuse surface layers with a high concentration of positive ions. The internal solution of the shaly reservoir rock has therefore a different ionic composition and concentration than the electrolyte with which it is in equilibrium (connate water produced from the formation or mud filtrate by which the formation is invaded). To calculate the equilibrium concentration of the internal solution, use is made of the Donnan6 relation, which states that the mean ionic activities of the internal solution and of the external electrolyte must be equal. From this and the

Jan 1, 1956

By J. C. McDonald

A DDITIONAL experimental data are presented in this note on a phenomenon which has been touched on but lightly in the literature. The common magnesium base rolling alloy (AZ31B) contains about 3 pet A1 and 1 pet Zn. When cold rolled, it hardens until it starts to break up in the rolls at 30 to 50 pet reduction. When it is heated after rolling to full hardness, it softens. However, other magnesium alloys have shown themselves capable of being cold rolled indefinitely, provided the ratio of roll diameter to starting gage is sufficiently high. As measured by the tensile test, these alloys actually soften when the reduction becomes large (60 to 90 pct). A subsequent heating at 300' to 500°F can produce hardening of this metal. Heating at higher temperatures (600' to 800°F) causes recrystalliza-tion and softening. Menzen' has shown that a magnesium base alloy can be cold rolled without intermediate anneals as much as 90 pet. The alloy studied, Mg-1.5 pet Mn, softened considerably between 20 and 90 pet reduction, as measured by tensile properties; a decrease in yield strength of 30 pet, and an increase in elongation from 3.2 to 16.7 pet (longitudinal direction of the sheet). However, Menzen gives no data on the reaction of this metal. to heating. Ansel and Betterton2 and Hurst and Hatch3 report a similar effect in Mg-1.5 pet Mn-0.1 pet Ca. Their data show an initial hardening, followed by softening. The former authors also show that the alloy softened by cold rolling will harden when heated at low temperatures, and that these effects are absent in Mg-3 pet Al-1 pet Zn. In the course of work4, 5 some years ago, the author observed similar effects with alloys containing cerium, thorium, or zirconium; but not with elements like aluminum, silver, or zinc. Table IA contains the results of an experiment which shows these effects rather well. A binary alloy with 0.3 pet total rare earths (Mischmetal* added) was rolled hot to 1/16 in. and then annealed to full softness by heating 30 min at 800°F. Rolling was continued at 1.5 pet per pass to 80 pet total reduction on 8 in. diam rolls. The metal was harder after 20 pet work than initially but, at 80 pet reduction, properties were back to their original values. Heating for 1 hr at 450°F produced about the same hardness whether the reduction was 20 or 80 pet. At intermediate reductions, the metal hardened, but not to as high values. Extensive cold rolling may also be carried out on metal hot rolled at temperatures sufficiently low to produce a semihard temper. Mg-0.6 pet Zr was rolled to 0.1 in. at 700° to 800°F, 30 pet per pass. As shown in Table IB, a further cold reduction of 85 pet, at 1.5 pet per pass, definitely softened the metal.

Jan 1, 1959

By James R. I. Henagan, William O. Crego

The Mamou Field, located in Evangeline Parish, La., is an elongated anticlinal structure on the downthrown side of a major east-west fault with oil and gas production from the upper part of the Wilcox formation. Two main producing horizons occur at an approximate depth of 11,500 ft and have been designated the Morein sand and the Deshotels sand. The upper sand (Morein) had an original bottom-hole pressure of 6,788 psig, which is some 1,500 psi above the normal pressure for that depth. Oil production with high gas/oil ratios and fluid analyses giving high shrinkage factors prompted a study of the reservoir in its early stages. The results indicated a closed reservoir producing under solution gas drive with low expected ultimate oil recovery. The early study of the Wilcox formation and its contained hydrocarbons resulted in the presentation of the data to the Department of Conservation of the State of Louisiana. with suggestions for field rules and a request for permission to inject extraneous water into the Morein sand. The water injection plans eventually led to complete unitization of working and royalty interests, to the construction of a gasoline plant, and to a central tank battery installation for the field. Deshotels sand wells were reworked to the Morein sand, and the water injection system was installed and ready for continuous operation in the early part of 1949. The injection of water was started in time to arrest the bottom-hole pressure decline at or near the bubble-point pressure. This injection was calculated to increase the ultimate recovery and to conserve natural resources. Pressure maintenance, the extraction of LPG products, and the sale of residue gas (early 1950) represent an attempt to produce an oil field with utmost efficiency. INTRODUCTION The two principal Wilcox oil horizons in the Mamou Field are the Morein sand and the Deshotels sand, occurring at 11,500 ft and 11,700 ft subsea, respectively. Minor oil production has been encountered in Morein stringer sands. (Fig. 1.) This paper deals only with the Morein sand, which is blanket over the Mamou Field. It is, however, segmented by the northwest-southeast "E" fault as shown in Fig. 2. The west segment is the area involved in the water injection pressure maintenance program. To date the east segment has operated largely under the influence of a strong water drive. The paper presents (1) a brief history of field development, (2) a resumé of reservoir conditions which led to the decision to inject extraneous salt water into the principal producing horizon, and (3) a summary of reservoir analysis and performance. FIELD DEVELOPMENT The Mamou Field is located in Evangeline Parish, La. The discovery well (J. B. Morein No. 1, now Unit No. 5) was completed in December, 1945, after penetrating 200 ft into the Wilcox formation. Initial production from the Morein

Jan 1, 1951

By James R. I. Henagan, William O. Crego

The Mamou Field, located in Evangeline Parish, La., is an elongated anticlinal structure on the downthrown side of a major east-west fault with oil and gas production from the upper part of the Wilcox formation. Two main producing horizons occur at an approximate depth of 11,500 ft and have been designated the Morein sand and the Deshotels sand. The upper sand (Morein) had an original bottom-hole pressure of 6,788 psig, which is some 1,500 psi above the normal pressure for that depth. Oil production with high gas/oil ratios and fluid analyses giving high shrinkage factors prompted a study of the reservoir in its early stages. The results indicated a closed reservoir producing under solution gas drive with low expected ultimate oil recovery. The early study of the Wilcox formation and its contained hydrocarbons resulted in the presentation of the data to the Department of Conservation of the State of Louisiana. with suggestions for field rules and a request for permission to inject extraneous water into the Morein sand. The water injection plans eventually led to complete unitization of working and royalty interests, to the construction of a gasoline plant, and to a central tank battery installation for the field. Deshotels sand wells were reworked to the Morein sand, and the water injection system was installed and ready for continuous operation in the early part of 1949. The injection of water was started in time to arrest the bottom-hole pressure decline at or near the bubble-point pressure. This injection was calculated to increase the ultimate recovery and to conserve natural resources. Pressure maintenance, the extraction of LPG products, and the sale of residue gas (early 1950) represent an attempt to produce an oil field with utmost efficiency. INTRODUCTION The two principal Wilcox oil horizons in the Mamou Field are the Morein sand and the Deshotels sand, occurring at 11,500 ft and 11,700 ft subsea, respectively. Minor oil production has been encountered in Morein stringer sands. (Fig. 1.) This paper deals only with the Morein sand, which is blanket over the Mamou Field. It is, however, segmented by the northwest-southeast "E" fault as shown in Fig. 2. The west segment is the area involved in the water injection pressure maintenance program. To date the east segment has operated largely under the influence of a strong water drive. The paper presents (1) a brief history of field development, (2) a resumé of reservoir conditions which led to the decision to inject extraneous salt water into the principal producing horizon, and (3) a summary of reservoir analysis and performance. FIELD DEVELOPMENT The Mamou Field is located in Evangeline Parish, La. The discovery well (J. B. Morein No. 1, now Unit No. 5) was completed in December, 1945, after penetrating 200 ft into the Wilcox formation. Initial production from the Morein

Jan 1, 1951

By Ronald C. Koo

THE effect of grain size on the mechanical properties of the bcc metals has been a subject of intensive theoretical and experimental study.'-l5 Quantitative relationships have been established experimentally between yield stress and grain size and between the ductile-brittle transition temperature and grain size in a number of metals.6"15 Much significance has therefore been attached theoretically to the grain size dependence. In all these experiments, different grain sizes were always achieved by annealing specimens at various temperatures. The implicit assumption was that any change in the dislocation substructure or in the distribution of impurities which might occur simultaneously with the production of various grain sizes had only a negligible effect on the mechanical properties. The validity of this assumption, however, is questionable. transformation in iron-nickel alloys is actually an extraneous phenomenon due to inadvertent compositional changes in the martensite if the heating rate is not sufficiently rapid. This complication can be avoided by up-quenching for the reversal treatment,5 and then the stabilization does not appear. Clearly, the lattice imperfections and strengthening produced by the reverse transformation are not responsible for the marked stabilization which has been observed by other investigators in these alloys. Data will be presented in this note to show that, at least in recrystallized tungsten of commercial purity, the difference in the ductile-brittle transition temperature of specimens annealed at various temperatures is more a result of a variation in the distribution of impurities rather than of the difference in grain size produced by the anneal. Ductile-brittle transition temperatures in tension were determined on powder-metallurgy tungsten specimens recrystallized at various temperatures. Tensile specimens having a gage length of 1.50 in. and gage diam of 0.18 in. were recrystallized at 1450°, 2000°, 2350°, 2550°, 2750°, or 2800" for 30 min in a vacuum furnace at a pressure of 1 x 10"5 mm of Hg and then tested at a constant extension rate of 8 x 10 per sec in an argon atmosphere from 100" to 800". Typical quantitative analyses of impurities are given in the Table. These results show that, within the precision of the analyses, see Table, annealing did not result in any detectable change in the impurity contents of the specimens, nor was there any detectable difference in purity between specimens having large differences in grain size annealed at the same temperatures . The results of the tensile tests yielded three distinct ductile-brittle transition curves approximately 225' apart. As shown in Fig. 1, data of specimens annealed at 1450°C and those of specimens annealed at 2000°C (O) fell on Curve A. Data of specimens annealed at 2350" and 2550°C fell on Curve B, and those of specimens annealed at 2750" and 2800°C fell on Curve C. The decrease in ductility with increase in annealing temperature became so pronounced that one third of the specimens annealed at 2750" and two thirds of the specimens

Jan 1, 1963

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942

By R. S. Silo

A new process for leaching oxidized copper ore (CuO) is presented. Its principle advantage is that it requires low cost raw materials. For large operations the only materials used are sodium chloride (NaCl) and calcium carbonate (CaCO3). In those operations of medium size, sulfur, which is abundant in the North of Chile, is used. However the process may also be applied to small copper plants provided low cost sulfuric acid is available as a substitute for sulfur. That is, it may be applied to those small capacity plants where large additional installations for the regeneration of the leaching solution are not needed. The method is comprised of six stages, namely: Crushing, Leaching, Washing of the Solution, Precipitation, Regeneration of the Leaching Solution, and Fusion. A flow diagram for this process in a large or medium-sized plant is given. LEACHING This process requires hydrochloric acid as the leaching solution for treating copper ores. This is easily produced from sulfuric acid and sodium chloride as follows: A small excess of NaCl is advisable to avoid the presence of free sulfuric acid. The experiments reported here were performed with 36 grams of HC1 per liter of solution to obtain a free acidity equivalent to 50 gpl of H2SO4 (the usual leaching solution concentration). Hydrochloric acid leaching may be done by either of the usual methods; i.e. percolation or agitation. The method selected depends on the characteristics of the ore. No matter which method is chosen, low pressure air can be used either as an air lift for circulation of the solution, or for agitation of the pulp with "Pachuca" tanks. In either case, there are no problems with respect to oxidation. Leaching by agitation produces good recovery; but at times, the problem of high consumption of leaching solution or the overproduction of grinding slimes which interfere with contact between phases negates this advantage. The percolation method was used in this study. Percolation took place in four 15-liter containers, 11 1/2 in. diam. by 12 in. height, having hemispheric bottoms. Each container was fitted with a wooden bottom having 1/4 in- holes. The air lift was a 3/4 in. plastic tube 10 in. high. Air at 6 psi was supplied from a rotating laboratory compressor. 10 kg of ore were charged to the container and counter-current leaching was used. The leaching solutions were fed through the center pipe in order to use the ascending solutions to reject the air in the charge. The solution circulated through the air lift in order to facilitate the movement according to the increase in density produced by the reaction between the phases present. Specific observations made in this report cannot be generalized because the leaching characteristics are dependent on the nature of the ore used, the method of leaching, and the production of primary or secondary slimes while crushing or leaching.

Jan 1, 1967

By W. F. Kieschnick, and W. J. McGuire&apos, Eugene Harrison

This paper concerns the induction and extension of fractures into rock formations as involved in drilling, completing, and production stimulating operations on wells. Conclusions concerning formation breakdown are derived from (I) a review and extension of published analyses relating to mechanical theories of rock stress and the state of stress in the earth's crust and (2) a correlation of field data from fracturing operations. Conclusions concerning the mechanics of fracture extension, which indicate the relationship between fracture dimensions and rock properties, depth, and volume of injected fluid, are tentative and largely establish limits of relationships. These conclusions are derived from stress calculations, limited field data, and laboratory experimental studies. The experimental work involves the study of the stresses at the fracture boundaries and the geometry of pressurized fractures by means of photo-elastic modeling methods. Results of this investigation indicate that a large majority of pressure induced wellbore fractures are vertical, particularly in deeper wells; and variations in the pressures necessary to create and extend fractures can be explained largely on a basis of established rock properties. It is also shown that variations due to tectonic forces should usually be expected to be slight. Other results indicate that during that extension of fractures rather large fracture volumes are temporarily created by the parting of the formation. The purpose of this paper is to present the results of calculations and laboratory experiments concerning the mechanics of fracture induction and extension with a view to broadening existing knowledge relating to these phenomena. It is believed that continued progress in developing knowledge of this type is important to the further development of techniques for drilling and completing wells. When a wellbore is subjected to sufficiently high pressure, fracturing of the formation surrounding the well occurs. This phenomenon is a common cause of lost circulation during drilling operations, is a deliberately planned factor in most squeeze cementing operations, and is the controlling factor in many productivity stimulation operations. The exploitation of formation fracturing in recent years has been particularly impressive in sand-viscous fluid well stimulation treatments which were first introduced to the industry by the Stanolind research group1,2,3 several years ago. The borehole fracturing phenomenon has been analyzed mathematically by application of the principles defining the elastic and inelastic behavior of thick-walled cylinders of homogeneous, isotropic, and impermeable material.1,5,6 This basic argument is re-presented in this paper along with new considerations which strengthen it. In addition to these arguments relating to fracture induction some calculations and experimental results relating to the mechanics of fracture extension are presented. Since the nature of the pressure induced fracture at distances from the well is of great importance in considerations of well stimulation procedures there appears to be a need for an integrated approach which deals with the mechanics of fracture extension as well as with wellbore rupture.

Jan 1, 1955

By Hjalmar W. Johnson

It has long been accepted that blastfurnace practice varies to some degree with the coke used. While the qualities desirablc in iron have been known for some time, the qualities in coke that produce such iron have not been established. There are no objective standards for blast-furnace coke, which is usually described in general terms, as good or bad. Many experienced operators believe that coke cannot be measured objectively except by using it in the furnace, noting the result, and labeling the coke according to furnace operations. This is admittedly unscientific, and besides is useless for the two main purposes for which a measure of coke quality is needed: (I) to produce the best possible coke from the coals and equipment on hand; (2) to test new coals and determine their value for blast-furnace coke. In seeking such an objective measure, much work has been done on tumbler tests, shatter tests, sizes of coke, porosity, specific gravity, reactivity or combustibility and other tests, but as yet very little has been published in which conclusive correlations have been established between such objective measures and furnace operation. In our study of the problem during the past 8 years we have developed no new measures of coke quality, but we have collected data that are presented here in the hope that they may assist in further work, so that at some future time there may be developed such positive measures. The purpose of this paper is to show that there are variations in coke and that such variations do influence the operation of blast furnaces. At the same time we must remember that there are variations in blastfurnace operation and it may be the blast furnace that is at fault. This correlation of coke properties with blast-furnace operation will be worked out in the following steps: . Discussion of a period when a change in the coke resulted in an increase in efficiency on one furnace and a decrease in efficiency on another. 2. Adaptation of the inefficient furnace to the available coke so that normal efficiency was restored. 3. The use of radial distribution: a discussion of the effect of size of ore layer in adapting blast-furnace operation to the coke. 4. An example of a change in size of coke and the detrimental influence on the pro duction of one furnace. 5. An example of a change in size of coke, together with manufacturing data, to show why it changed, the conclusion being that coke is a product with an optimum value. 6. Illustration of the fact that coke has different optimum values on two furnaces, with discussion on adaptation of operation so the optimum values will be the same. 7. Limitations of the use of screen tests as an objective measure of coke quality. 8. Importance of uniformity in coke. Functions of Coke and Qualities Required to Perform These Functions Coke has three important functions in a blast furnace: (I) to furnish most of the

Jan 1, 1942

By Hjalmar W. Johnson

It has long been accepted that blastfurnace practice varies to some degree with the coke used. While the qualities desirablc in iron have been known for some time, the qualities in coke that produce such iron have not been established. There are no objective standards for blast-furnace coke, which is usually described in general terms, as good or bad. Many experienced operators believe that coke cannot be measured objectively except by using it in the furnace, noting the result, and labeling the coke according to furnace operations. This is admittedly unscientific, and besides is useless for the two main purposes for which a measure of coke quality is needed: (I) to produce the best possible coke from the coals and equipment on hand; (2) to test new coals and determine their value for blast-furnace coke. In seeking such an objective measure, much work has been done on tumbler tests, shatter tests, sizes of coke, porosity, specific gravity, reactivity or combustibility and other tests, but as yet very little has been published in which conclusive correlations have been established between such objective measures and furnace operation. In our study of the problem during the past 8 years we have developed no new measures of coke quality, but we have collected data that are presented here in the hope that they may assist in further work, so that at some future time there may be developed such positive measures. The purpose of this paper is to show that there are variations in coke and that such variations do influence the operation of blast furnaces. At the same time we must remember that there are variations in blastfurnace operation and it may be the blast furnace that is at fault. This correlation of coke properties with blast-furnace operation will be worked out in the following steps: . Discussion of a period when a change in the coke resulted in an increase in efficiency on one furnace and a decrease in efficiency on another. 2. Adaptation of the inefficient furnace to the available coke so that normal efficiency was restored. 3. The use of radial distribution: a discussion of the effect of size of ore layer in adapting blast-furnace operation to the coke. 4. An example of a change in size of coke and the detrimental influence on the pro duction of one furnace. 5. An example of a change in size of coke, together with manufacturing data, to show why it changed, the conclusion being that coke is a product with an optimum value. 6. Illustration of the fact that coke has different optimum values on two furnaces, with discussion on adaptation of operation so the optimum values will be the same. 7. Limitations of the use of screen tests as an objective measure of coke quality. 8. Importance of uniformity in coke. Functions of Coke and Qualities Required to Perform These Functions Coke has three important functions in a blast furnace: (I) to furnish most of the

Jan 1, 1942

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Cryolite, sodium aluminum fluoride, Na3AlF6, is a rare mineral which has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. History Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in sixteenth century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open-hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and II. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940s were outstanding technological advances that facilitated increased production. Recently, pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. Uses of Fluorspar Fluorspar is used to make hydrogen fluoride, also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride (HF) is produced by reacting acid grade (97% CaF2) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation, the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, which is an ingredient in high-octane fuel for aircraft and automobiles, in steel pickling, enamel stripping, glass etching and polishing, and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 50 to 60 lb of fluorine content in synthetic cryolite and alumnium fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly.

Jan 1, 1983

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to 1706°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous days burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the day, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By H. W. Hitzrot, R. H. Limons, L. V. Fegan

The testing of a new method for measuring pellet-bed temperatures in the traveling-grate or shaft furnace is presented in this paper. This method, using silver-palladium alloy wires as indicators, overcomes disadvantages existing in the methods based on the use of thermocouples which are costly and time-consuming. The authors have developed and tested a new method for measuring pellet-bed temperatures in the traveling-grate or shaft turnace through the use of silver-palladium alloy wires as indicators. This method overcomes the disadvantages of existing methods, which, based on the use of thermocouples, are generally costly and time-consuming. For example, in the case of the traveling-grate furnace, the installation of an instrumented pellet, together with its attached thermocouples, requires stopping the furnace, with resulting loss of production time. As for temperature measurement in the shaft furnace by the existing method, the movement of the shuttle-car feeder seriously interferes with both the actual insertion and the resulting distribution of continuously fed thermocouples. The authors have overcome these difficulties by using, as temperature indicators, a range of silver-palladium alloy wires that can be easily recovered, after firing at any desired location in a pellet furnace. Silver-palladium wires having specific melting points from 2000°F to 2500°F are enclosed in ceramic capsules. Each capsule is placed in a ni-chrome wire basket filled with a sample of green pellets, the baskets being the means for recovering the capsule after firing. After the encapsulated wires have been exposed to the firing cycle, the alloy wires are examined to determine the maximum temperatures attained by the pellet sample. This method gives accurate, rapid determinations of maximum temperatures attained during pellet induration in either the traveling-grate or shaft furnace The new method has the following advantages over existing methods: 1) it is less expensive; 2) no furnace downtime is required; 3) the testing units can, be made in quantity in advance; 4) measurements can be made in rapid succession at all desired locations; 5) measurements of maximum firing temperatures are more accurate; 6) on the basis of points 4 and 5, the new method gives a more reliable picture of the correlation of pellet quality, petrographic textures and maximum temperatures, thus providing a more effective quality-control tool. A disadvantage of the method is, of course, that the measurements are not continuous and only maximum temperatures are determined. TEST PROGRAM Preparation of Materials: CALIBRATION OF ALLOYS - In the following discussion the term "bead point" (see Fig. 1) refers to the temperature at which each alloy begins to melt and form a bead. Fig. 2 gives the bead point curve for silver-palladium alloys. Before the alloys are used in plant tests, the bead point of each alloy should be determined in the laboratory to verify the alloy compositions. Once a given alloy has been calibrated, it can be

Jan 1, 1965

By Fred C. Bond

MANY grindability tests have been made in the Allis-Chalmers laboratory since the tabulated results were last published.1 The lists of standard ball-mill and standard rod-mill grindability tests are brought up to date in this paper, and considerable new material is added. This includes a tabulation of open-circuit grinding tests, with impact and compression-crushing tests. The standard ball-mill grindability tests (Table I) were made in a standard laboratory ball mill, 12 by 12 in. inside, running at 70 rpm, with a charge of 285 iron balls ranging from 1 1/2 to 3/4 in. in diameter and weighing 20,125 grams. Seven hundred cubic centimeters of minus 6-mesh stage-crushed dry feed was used, and the circulating load was maintained constant at 250 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 28 to 200, and the grindability is the number of net grams of screen undersize produced per revolution. The table includes 479 tests. It has been calculated that the ball mill does 52.3 joules of useful work on the ore per revolution2 with 93 joules input to the mill. The standard rod-mill grindability tests (Table 2) were made in a laboratory tilting rod mill, 12 in. in diameter by 24 in. long inside, with a wave-type lining, running at 46 rpm. The grinding charge consisted of six 1 1/4-in. diameter and two 1 3/4-in. diameter steel rods, all 21 in. long and weighing 33,380 grams. The mill was rotated level for eight revolutions, then tilted up 5° for one revolution, down 5° for one revolution, and returned to level for eight revolutions. It was discharged by tilting downward at 45° for 30 revolutions. Feed consisted of 1250 cc of minus 1/2-in. stone and the circulating load was maintained constant at 100 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 3 to 65, and the rod-mill grindability is the number of net grams of screen undersize produced per revolution. The table includes 105 tests. The impact and compression-crushing tests (Table 3) are given in a table that is an extension of a previous publication3 in which the method of testing was described in detail. Two equal hammers weighing about 30 lb each were arranged to strike simultaneous blows on opposite sides of the test specimen. Broken pieces of rock passing a 3-in. square and retained on a 2-in. square were set up with the smallest dimension between the hammers, and this distance was measured. The height of the hammers was increased slightly before each blow until the specimen broke, and the foot-pounds per inch of thickness was calculated. Ten pieces

Jan 1, 1947