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By d&apos, John C. Entremont

Pure iron was inductively melted in small refractory crucibles and optical pyrometer and immersion thermocouple readings were simultmzeously taken. The resulting emissivities of the liquid iron surface obtained were found to be greatly affected by both the gaseous atmosphere and geometrical changes in the physical setup. Quantitative values for these effects are indicated. FOR many applications in both the laboratory and plant, optical pyrometry is still the best means of measuring temperatures in the incandescent range. A prerequisite in evaluating the correct temperature is a good value of the emissivity of the surface. To obtain the emissivity from the tabulated values of the literature can be very confusing and often far from correct. There are many reasons for these difficulties, and it is not within the scope of this paper either to enumerate or to discuss them all. Its purpose is to show quantitatively how several factors affect the apparent emissivities obtained from experimental measurements on liquid iron surfaces. The black body is the reference state for the quantitative values of emissivities and is defined1 as a body which absorbs all radiation incident on it, reflecting none; such a surface emits more radiation per unit area per unit time than any surface which reflects any radiation, and is given a value of unit emissivity. All bodies having reflective power thus have emissivities less than unity and are considered nonblack or grey bodies. The ratio of the radiant energy emitted by the flat, nonblack surface to that of a perfectly black surface of equal area and temperature is the emissivity of the surface. The above definitions are applied to flat, polished, opaque surfaces, very seldom encountered in actual measurements, and for this reason many authors have suggested that the word "emittance" be used for real bodies rather than emissivity. The emittance has reference to the material and its configuration rather than to its properties in the idealized state. Recent observations of molten iron in a small refractory crucible indicate that not only the configuration of its surface but the geometrical arrangement of its surrounding and the nature of the surrounding atmosphere have a pronounced effect on the emittance. Neglect of changes in such conditions may lead to errors as large as 40°C at 1600°C. Thus it is suggested that the term "apparent emissivity" be used and that it be recognized that its value pertains to a particular experimental arrangement only. As a result of not recognizing these differences in emissivities, which are obtainable from changes in the physical setup of an observation, many investigators have incorrectly quoted their values as those of the emissivities of particular materials rather than as an apparent emissivity for their particular arrangements. As a consequence, values of the emissivity of liquid iron ranging from 0.3 up to 0.55 are found in the literature. In an effort to establish an accurate optical temperature scale for liquid iron solutions in which de-oxidation studies were to be carried out, it was observed that the temperature relationship, obtained by simultaneously taking immersion thermocouple

Jan 1, 1963

By H. Buttner, F. H. Udin, J. Wulff

GRAIN boundaries, the interface between adjacent crystals differing only in respective orientation, have been the object of much experimental and moderate theoretical attention for many years. The earlier experimental work was primarily concerned with the effect that grain boundaries have on the physical behavior of metals, while the basic nature of the boundaries themselves drew only secondary attention. A complete turnabout has been witnessed in more recent years, however, as researchers are now undertaking investigations bearing as directly as possible on the character and physical properties of the grain boundary. Quite comprehensive reviews of the past literature on the subject of grain boundaries have been reported on numerous occasions by various authors, and together these references represent a thorough coverage.'-? It becomes evident in these reviews and other papers"" that the properties of grain boundaries can be explained by regarding a grain boundary as a crystalline region of transition between two unmatched grains. Studies show that grain boundaries have a definite interfacial energy. By measuring the geometry about a point where three interfaces meet in equilibrium, the energy of any two boundaries can be measured with respect to the third. If the absolute interfacial energy of one boundary is known, the absolute energy of the other two boundaries can be calculated. This apparently holds true for any system of phases and interfaces.""25 Most studies have been carried out on solid-solid or liquid-solid systems, or systems of both. However, if about the point of intersection one phase is vapor and the other two are disoriented grains, then two interfaces are surfaces, and one is a grain boundary. Investigations leading to relative grain boundary energy for this particular system have been made by Fullman,23 Greenough and King," and Bailey and Watkins." Herring" treats the system mathematically and arrives at an equation, which appears as Eq. 1, in a form consistent with the reference angles indicated in Fig. 1, ( d?1 ?n = x sina + cosa ( ------- 2 ?2 Sinß da + C0Sß (d?2/d As the system of interfaces comes to equilibrium, a groove of angle appears at the intersection of the grain boundary with the surface, an effect first observed by Rosenhain and Humfrey." Eq. 1 is essentially a summation of the vertical components in Fig. 1 set equal to zero, where ?1 and ?2 are surface tension vectors lying along the side of the groove at point 0 in the groove root. The differential vectors represent the forces tending to rotate the surface into a position that will expose a crystal cleavage surface of lowest energy. Chalmers, King, and Shuttleworth- simplify Eq. 1 by assuming the differential vectors equal to zero, ?1 = ?2= ?Surface and arrive at the following equation: ?B = 2?s cos [2] Greenough and King24 use Eq. 2 for determining the grain boundary energy of silver using prepared bi-crystals of known orientation. Bailey and Watkins25 have done the same for copper, as did Chalmers and others on lead. These authors report the grain boundary values as ratios relative to the surface energy. In the above work, the orientation of grains forming the grain boundary in all cases was controlled so

Jan 1, 1954

By E. P. Abrahamson

The effect of transition element binary solid solution additions upon the re crystallization temperature of nickel has been investigated. All additions raised the re crystallization temperature. Both the rate of change of re crystallization temperature with at. pet solute and the limit of initial linearity are found to correlate with the free atom ground state outer electron configuration of the solute element. A comparison of all of the correlations for the transition elements studied has yielded a set of empirical relations, which allows the prediction of the effect of dilute binary transition elements on the recrystallization temperature of other transition elements. The work of Abrahamson, et al.1-7 on dilute binary solution alloys indicated a correlation between the free atom ground state electron configuration of the solute and both the brittle-ductile transition and re-crystallization temperature. Further, it has been shown3,4 that the limit of initial linearity may also be correlated with the solute electron configuration. Since previous studies have dealt with bee and hexagonal base elements, this study is made to note what effect, if any, the fee base structure might have. Nickel also serves to give a solvent configuration which will allow the comparison of all of the transition element solvents. Olsen8 has studied the effect of some trace elements upon the recrystallization of nickel. He included only Ti, Zr, W, Mn, and Co of the transition elements. The differences in change of recrystallization temperature were attributed to the solute atom size and to the solubility of the solute in nickel. PROCEDURE All alloys were made using 99.9 + pet Ni with 0.003 C, 0.015 Fe, 0.007 0, and 0.0007 H. The solute elements were 99.9 + pet pure. According to the published binary phase diagrams9 and metallo-graphic examinations at X750, all solute elements were in solid solution. The alloys were arc melted and remelted four times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot forged at 800oC to 0.750 in. diam, machined to 0.60 in., vacuum annealed for 1 hr at 700°c, swaged to 0.40 in. and annealed at 700oC for 1 hr in vacuum. The grain size was checked and found to be 77 * 20 grains per sq mm. The specimens were then swaged to 0.187 in., yielding 76 ± 1 pet cold work. All alloys were then chemically analyzed for the solute addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The swaged rod was cut into 8.25 in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was maintained at 250" to 850°C over an eight inch length, recorded by twelve thermocouples. Control was ± 3oC, accomplished at the hot end. The recrystallization was determined metallo-graphically over the entire specimen. The criterion chosen was that point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be generally ± 3oC.

Jan 1, 1962

By L. S. Darken

It has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernstl in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and FuossZ with results which have recently been confirmed experimentally by Harned and Nuttall. This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author,4,5 who pointed out4 that "for a system of more than two components it.is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepti- cism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley" in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion of acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 10500 C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1949

By Orville R. Lyons, A. C. Richardson

THE Coal Division of Battelle Memorial Institute, during the course of an investigation conducted for a coal producer, carried out extensive sampling of the fine-coal section of a preparation plant. The information obtained during the testing period was used to evaluate the overall plant operation and provided the basis for. recommended changes in the plant flowsheet. Included in the information were data for the results obtained when using a Bird centrifuge to dewater the particular coal being treated. At the completion of the investigation, the coal producer gave Battelle permission to publish the operating data for the Bird centrifuge in order to make this information available to the coal industry. The authors wish to take this opportunity to express their appreciation to this company and its officials for their willing cooperation in the matter of publication. Description of Preparation Plant: The preparation plant on which the data were obtained is primarily a jig plant. The coal being washed is a low inherent moisture, friable, Pocahontus-type. The washed coal from the jig is dewatered and sized at 1/4 in. by a Parrish-type dewatering and sizing screen. The minus 1/4-in. coal and the underflow water from the shaker screen flow to a sludge tank where, after the coal settles, the coal is conveyed by a flight conveyor into a pump sump. The pump, a 300-gpm sand pump, delivers a mixture of fine coal and water to a Bird centrifuge which produces a dewatered cake and an effluent. At the time when the investigation was made, the centrifuge effluent was returned to the sludge tank and the cake product was mixed with a coarser size of coal prior to loading into railroad cars. The semiclarified water from the sludge tank overflowed into a pump sump from which it was pumped to the jig. As originally designed, the preparation plant was intended to operate with a closed water system but it was found, soon after operations started, that for various reasons this could not be done. In order to provide for removal of excess water from the system and to aid in maintaining the desired minimum percentage of solids in the circulating water, the plant was operated to provide from the sludge tank a continuous overflow of water and fine solids that was sent to waste. The centrifuge feed represents approximately 35 tons per hour of minus 1/4-in. coal in the form of a pulp averaging 38 pct solids. Sampling Procedure: In order to obtain basic data for determining the relationships existing in the fine-coal section of the preparation plant, samples were obtained for: (1) the centrifuge feed, (2) the centrifuge cake, (3) the centrifuge effluent, and (4) the circulating water. The sampling was arranged to start on a Monday, in order to begin operations with a sludge tank full of fresh water, and was continued long enough to allow sufficient time for fine solids to build up within the water system or for a two-day, four-shift operating period. All samples were taken at half-hour intervals except when plant stoppages occurred. After a stoppage the plant was

Jan 1, 1951

"The 100,000 volt sub-station at Butte is located near the center of the district in which the power is distributed. The sub-station building is 150 feet by 50 feet in plan and 50 feet high. It is a brick walled, steel framed structure with concrete floors and roof.There are installed at present four banks of single-phase transformers, rated at 3,600 k-w. per bank and connected in delta on both high and low tension sides. They step the voltage down from 102,000 to 2,500, at which voltage it is distributed to customers. The transformers are installed in fireproof compartments, entirely shut off from the rest of the building by brick walls and opening only out of doors. The transformers are mounted on wheels and can readily be run out onto a flat car, which stands on a track running parallel with the building in front of the row of transformer compartments. This arrangement furnishes a convenient method of handling the transformers, both at the time of installation and afterward, in case it is necessary to make repairs."

Jan 1, 1913

By L. J. Boucher

The beneficiation process at Northampton is described and reasons are given for installing a flotation plant. The economics of running the plant, the difficulties of operation, and subsequent remedial action are discussed. CEMENT rock from a quarry operated by the Northampton plant1, 2 of the Universal Atlas Cement Co. has a relatively low average CaCO³ content. To meet specifications required for cement manufacture it was formerly necessary, over succeeding years, to add increasingly larger amounts of high-lime, low-alumina rock, which was obtained from a quarry operated by the company at a point along the New Jersey-New York state border, 79 miles from Northampton. Previous to 1940, 8 pct of total kiln feed consisted of high-lime rock. From 1940 to 1943, this figure jumped to 13 pct. Today it would be necessary to use 18 pct of this high-lime to meet current specifications. Increasing transportation costs made this an expensive operation. In addition, this high-lime rock quarry was contaminated with granite and high magnesia pockets. As there was no available high-lime rock in the Lehigh Valley, it was decided in 1936 to install a pilot plant where experimental work was done on processing local cement rock with flotation and burning the resulting product in a small kiln. This plant was in operation for six months and at the end of that period a suitable method of flotation had been established. From these studies it was also found that if the proportion of shipped-in rock rose slightly above 10 pct it became economically advisable to use the flotation process. It is the object of this paper to present briefly the operation of the flotation system at the Northampton plant. It seems advisable to comment on the raw material used in this process. The Northampton quarry lies geologically in what is known as the Jacksonburg formation of Trenton limestone.' In Pennsylvania this extends in a southwesterly direction from Portland, through Nazareth, Bath, and Northampton and across the Lehigh River to Ormrod. This argillaceous limestone was formed from marine deposits laid down during the early Ordivician period when a shallow sea covered most of Pennsylvania. Carbonaceous matter in the original deposit formed graphitic carbon under later metamorphic forces. From this graphite the cement rock of the Lehigh Valley derives its dark color. Most of the graphite must be removed before lime flotation can proceed. The quartz in this rock is desirable from the chemist's point of view, as it furnishes him with a form of silica necessary in the calcining process, but its abrasive properties damage pumps and piping. Aluminum silicates of potassium, sodium, iron, and magnesium are found in the form of sericite. Cal-cite averages from 69 to 76 pct. Iron in the form of iron pyrites is also present and has no deleterious effect. Talc is present in minute quantities. The

Jan 1, 1954

By S. Shapiro, R. G. Ames

Background Research on the respiratory health of coal miners has focused predominately on the relationship between coal mine dust exposure and ventilatory function impairment (Lapp et al., 1972; Jacobsen, 1976), on the prevalence of coal workers' pneumoconiosis (Lainhart et al., 1969; Morgan et al., 1973), and on coal miner mortality (Ortmeyer et al., 1974; Rockette, 1977). Lesser attention has been paid to the effects of other mining exposures. For example, underground exposure to diesel exhaust emissions (Reger et al., 1980; Ames et al., 1982,1984). An omission in US coal mining research, however, has been identified by the US Office of Technology Assessment (OTA) as the failure to study the effects of inhaled polyvinyl chloride (PVC) thermal decomposition and combustion products (Seltzer, 1979). These products may be released in the mine environment by cable fires, cable explosions, smoldering cables, and conveyor belt fires. In addition to the OTA concern, recent findings of chronic respiratory conditions and other health complications resulting from exposure to PVC decomposition and combustion products in firefighters (Peters et al., 1974; NBS, 1980; NIOSH, 1982; Wallace, 1982), and in survivors of several large scale PVC-fueled fires (Dyer and Esch, 1976; Wallace, 1981, 1982), add immediacy to the concerns. PVC decomposition and combustion PVC decomposition is initiated at temperatures far below ignition (Hartstein and Forshey, 1974; Wallace, 1981). Hence, exposures to decomposition products from smoldering cables may be important health hazards in addition to cable insulation combustion products. Hydrochloric acid (HCL) appears to be the principle toxic substance from the thermal decomposition of PVC since up to 60% by weight is released as HCL (Barrow et al., 1979). HCL is released both as a gas and as an adsorbant on soot particles (Stone et al., 1973), thus allowing penetration of respiratory defenses. In addition, laboratory results indicate that phosgene (carbonyl chloride), a potentially lethal gas, may be produced in significant quantities from electrical arcing of wires covered with PVC insulation (Woolley, 1971; Brown and Birky, 1980). Health concerns related to PVC Toxic effects resulting from high level exposures to PVC pyrolysis and combustion products in animals (Cornish and Abar, 1969) and in humans (Wallace, 1981) is beyond question. Analyses have reported acute, or short-term, health effects resulting from exposure to PVC decomposition and combustion products (Peters et al., 1974; Polakoff et al., 1975). Recently, however, several studies have found that acute effects are often followed first by apparent healing, and then by delayed chronic effects. This pattern of consequential respiratory involvement among persons involved in major PVC-fueled fires has been noted in firefighters, specifically the 1975 New York Telephone Exchange fire (Dyer and Esch, 1976; Wallace, 1982), and the survivors of the 1977 Beverly Hills Supper Club fire (Wallace, 1981). An obstructive syndrome (low FVC and FEV1) was seen in 15% of workers three months following fighting a PVC-fueled fire (Colardyn et al., 1976). Long-term respiratory symptoms seen in studies of survivors of PVC-fueled fires include the bronchitis symptoms of cough and phlegm, and lung dysfunction (Wallace, 1981). Additional support for the thesis of longer-term respiratory effects resulting from PVC-fueled fires is derived from the finding that four persons who initially survived the Beverly Hills Supper Club fire died within nine months of the fire of severe respiratory impairment (Wallace, 1981).

Jan 1, 1986

By A. J. Teplitz, J. K. Rodgers, E. M. Pohoriles

This note is presented in order to call attention to a newly developed laboratory apparatus that appears to have interesting possibilities for the study of lost circulation of the pressure-parting type, for a more realistic evaluation of sealing materials for this type of loss, and for investigation of other aspects of hydraulic fracturing. A study of lost circulation, conducted jointly by operating divisions of the Gulf Oil Corp. and the Gulf Research & Development Co., has been in progress for the past few years. Earlier phases of the study dealt with mechanical factors contributing to loss of returns in laminar type sediments.' One aspect of this type of loss which has been widely discussed in the literature and elsewhere concerns the geometry of the fractures into which such losses occur. This subject is not merely a philosophical one, but has an important bearing on procedures for combating lost circulation difficulties and on other well operations. The further course of the collaborative studies previously mentioned has produced some information on this subject which, though limited in amount, is believed to be significant. In several typical cases of lost circulation in laminated shale and sand formations, the wells have been surveyed with instruments2,3 capable of detecting the points of loss with considerable accuracy. These wells were located in the Gulf Coast of Texas and Louisiana, in the Texas Panhandle, and in the Rocky Mountain area. In each of these instances the loss was shown to be occurring at some distance removed from the bottom of the hole and sharply confined to a very narrow interval, less than 1 ft in thickness. It is rather difficult to imagine that fractures of a vertical nature' would be of the limited extent indicated by the surveys in these wells. Furthermore, the high rates of loss at relatively low pressure differentials observed in some of these instances together with the narrow intervals involved would appear to require the radial flow pattern which would be associated with a more or less horizontal fracture plane. In view of the foregoing observations and records of successful squeeze cementing operations, in attempting to construct a laboratory apparatus For simulating pressure induced lost circulation, it was decided that the design should be based on a horizontal type of fracture. It was realized that5,6 Vhe production of horizontal fractures in a formation with non-penetrating fluid requires some mechanism for transmitting vertical components of the hydraulic forces to the plane of parting. This was accomplished, as will be evident in the description of the apparatus that follows, by providing recesses in the wall of the borehole which are believed to be representative of wellbore configuration found in Gulf Coast wells. The possible influence of such borehole irregularities on both pressure fracturing and the treatment of lost circulation appears to have been neglected in many studies of these subjects. It is believed that the present apparatus, incorporating features that take into account some of the factors mentioned, will provide means of gaining a further understanding of pressure induced fracturing and possibly for more realistically evaluating the numerous sealing agents, particularly the non-time-setting materials employed in treating the pressure-parting type of loss. DESCRIPTION OF APPARATUS The test cell used in the laboratory investigations is shown in Fig. 1. A schematic diagram of the entire system is shown in Fig. 2.

Jan 1, 1956

By Jens P. Nielsen, W. H. Justice

This paper describes an improved acidizing technique which has been applied in acidizing gas wells in the La Gloria Field. Wells acidized in this manner exhibited a much greater increase in deliverahility than wells acidized in the conventional manner. The acid is injected into the well in small slugs separated by a small volume of high pressure gas. The acid and gas are displaced from the tuhing by high pressure gas to reduce the hydrostatic head on the well when the acid is recovered from the well. The well is opened for production as soon as the acid and gas are displaced. This procedure permits a very rapid recovery of the acid which results in large increases in the deliverability of the gas wells. It has been found advantageous in the acidization of gas injection wells to inject the high pressure gas directly after the acid without backflowing the acid out of the well. This practice has made it possible to inject the gas in the injection wells of this field with a much lower pressure differential. This reduces the horsepower required to inject the gas and also decrease:, the number of injection wells required per reservoir. INTRODUCTION The results obtained by acidizing gas wells ill the La Gloria Field have varied considerably in the past. For this reason. a planned study of the acidizing procedure was undertaken in order to obtain more consistent results. The Frio Sands of the La Gloria Field are rather permeable and it was not necessary to acidize many of the wells when they were originally completed. At the completion of an eight-year cycling program in several of the gas reservoirs, it became necessary to recomplete many wells in other reservoirs. It was found that the opan Flow potential of the wells recompleted in different sands was not as large as wells that were originally completted in that reservoir. A study of the drilling records of several of these wells indicated that the sands had originally been subjected to considerable hydrostatic drilling fluid overload while the well was being drilled to the deeper sands of the field. It is indicated that during this eight-year period, the drilling mud and water that were lost into the formation when the well was being drilled had formed a relatively impermeable Eone around the well bore. This impermeable zone around the well bore made it very difficult to obtain high deliverability wells when the original wells are recompleted in other zones. Muskat' has shown that in uniformly permeable and porous formations a zone of partial plugging one ft in radius around the well would drastically decrease the productivity of the well. The analysis for this problem shows that the production capacity of a well is very sensitive to the value of the permeability of the zone immediately surrounding the well bore. This is to be expected in view of the highly localized character of the pressure drop in a radial flow system about the well center. The reduction of the deliverability is not proportional to the thickness of the mud-affected zone as the major portion of the reduction in deliverahility IS caused hy the

Jan 1, 1952

By Harry M. Mikami

Refractories are heat-resistant, generally nonmetallic materials used as the linings of furnaces or high temperature vessels in the steel, iron, nonferrous metals, glass, cement, lime, ceramic, chemical, petroleum, paper, and power and heat generation industries. Refractories must have structural strength at high temperatures but also, in many applications, must simultaneously resist chemical-physical corrosion-erosion from stags, metals, granular solids, or gases. Among the major uses are the pyrometallurgical processes for producing iron, steel, copper, aluminum, nickel, lead, zinc, etc. Rotary cement kilns, glass tanks, refineries, utility boilers, chemical and ceramic (including refractories) plants, and a myriad of other smaller scale users employ refractories in the high temperature parts of their operations. Thermal, chemical, and structural conditions under which refractories are used differ widely so there is a great variety of refractories to fill the various needs. Two major classifications are the "basic" and "acid" types. Basic refractories include magnesia and chromite, singly and in combinations, dolomite, and forsterite (olivine). The acid category includes aluminosilicates, alumina, and silica. There are a number of other specialized types such as carbon, graphite, silicon carbide, zircon, and zirconia that have important applications but are used in much smaller amounts than the major categories. Physically, refractories can be divided into bricks and shaped products on the one hand and unshaped or monolithic products (also termed specialties) on the other. There are many further subclassifications and divisions, a discussion of which is beyond the scope of this chapter; see Refs. 2 and 9. Raw materials for the principal basic refractories are magnesia and chrome ore. Magnesia, generally termed magnesite or periclase, is obtained mainly from seawater or saline brines extraction, but substantial amounts are produced from mined magnesite (MgCO3). Dolomite (CaCO3•MgCO3), another important basic refractory, is obtained entirely from mined sources. Acid refractory raw materials are: fire clays, flint clays, kaolin, and other natural clay minerals; aluminosilicate minerals such as kyanite, andalusite, sillimanite, pyrophyllite, bauxitic clays; calcined refractory grade bauxite, alumina from the Bayer process for the alumina group; and quartzitic rocks for silica refractories. The total value of all refractories shipped in the United States in 1974 was $989 million, a record to that date. Of this amount, about 73% represents bricks and shaped products and 27% is in nonshaped or monolithic products which comprise mortars, cements, castables, plastics, and ramming and gunning mixes. Fig. 15.4E.1 shows the rising value of all U.S. refractory shipments in the period 1948-1974. Values of brick and shapes paralleled

Jan 1, 1976

By R. P. Thomas

Secondary fertilizer minerals are the mineral materials used to supply directly and indirectly the secondary and trace plant food nutrient needs of a fertilizer. Since few soils contain sufficient availability of all plant nutrients for their proper growth, man has prepared mixtures of plant food materials to correct these nutrient deficiencies. These mixtures or fertilizers, when added correctly to a soil, make it possible for abundant and economic crop growth. Many kinds of materials are used as sources of these needed nutrients. They come from natural and synthetic materials and minerals including many beneficiated byproduct compounds. A fertilizer consists largely of carriers of one or more of the three major plant foods, namely nitrogen (N), phosphorus-phosphorus pentoxide (P2O5) and potassium-potash (K2O). Many other nutrients are just as essential for plant growth as the three major plant foods. In fact, the efficient use of fertilizers today depends upon an adequate supply of all these other nutrients. Since these additional materials are usually removed from the soil by plants and supplied in fertilizer in less quantities than the major nutrients, they are called secondary and minor nutrients. In the early days these special nutrients were contained as impurities in the primary nutrient carriers. Today, fertilizers are made primarily from concentrated and synthetic materials which carry very few of these other essential nutrients. Consequently, many secondary and trace nutrient carriers, as salts, byproduct compounds and even minerals have to be added to fertilizers. Secondary Nutrient Carriers The secondary plant foods in fertilizer are next to the major nutrients in abundance. They are calcium, magnesium, sulfur, chlorine, silicon and sodium. Although many of these elements are added to a fertilizer as part of the major nutrient carriers, they are also added in special carriers. The large tonnage of these secondary nutrient carriers used in fertilizers represents only a small percentage of the total production of these materials. A fertilizer producer thinks in terms of materials which supply nutrients instead of minerals. Therefore, these materials will be discussed by elements. CALCIUM Soils need calcium to supply the nutrient needs of plants and maintain the desired physical and biological conditions in the soil. The available calcium is usually 40 to 80 pct of the exchangeable bases. (These bases are ones which can be displaced by other cations and determined quantitatively. They are then expressed as milliequivalents per hundred grams of soil-me.) Direct applications of lime materials such as burnt, ground or hydrated limes are the important sources of calcium for the soil. Most crops, especially legumes, have a high requirement for calcium. The average farmer does not use enough lime to maintain the proper level of available calcium. Hence, it is necessary for many fertilizers to contain soluble calcium materials for efficient use of the major nutrients. The following major nutrient carriers supply some calcium: calcium nitrate, ammonium nitrate mixtures and cyanamid, and many of the phosphates. Both synthetic and natural gypsum are used in fertilizer production. Some crops such as peanuts require a large amount of soluble calcium. Gypsum is the important supplier of this soluble calcium. It is not applied with the fertilizer

Jan 1, 1960

By M. Muskat, H. H. Evinger

A methoD of calculating productivity factors for oil, gas, and water systems in the steady state is presented as an illustration of the quantitative application of the fundamental data on the flow properties of heterogeneous fluid systems. While the numerical results of the calculations cannot be applied directly to field conditions, because they are based on permea-bility data for unconsolidated sands and involve specific assumptions regarding the nature of the reservoir fluids, the methods of analysis and interpretation should havc significance in considering certain specific field situations when the necessary field and laboratory data become available. Moreover, it is felt that even under the idealized conditions to which the numerical calculations refer they should serve to give at least the orders of magnitude of the effects of gas-oil ratio and connate water on observed productivity factors. Within the indicated limitations, the computations imply that the foregoing factors can explain only a part of the apparent discrepancy between the homogeneous fluid productivity factors and those obtained recently in field measurements on the West Coast. IntroductioN Sufficient laboratory research has been carried out in the last several years on the fundamental features of the flow of heterogeneous fluids through porous media to call for consideration of what can be done with this type of information. It has, of course, already led to a, much clearer general understanding of the mechanics of oil production. However, examples of the quantitative application of the results of such laboratory studies are few in the literature. part of the explanation for this fact lies undoubtedly in the lack of sufficient laboratory data relating to practical fluids and sand systems such as would occur ill actual oil reservoirs. However, unless it can be shown that if such data were obtained quantitative applications could be made, serious doubt may be cast upon the desirability of carrying on further extensive experimental research work on fluid flow. The purpose of this paper is to present one approach to the problem of quantitative application of laboratory data to practical field problems. Because the published results on the basic experiments with three-phase fluid systems in porous media are limited entirely to uncon-solidated sands, the numerical applications made here will not pertain directly to any actual field situation. However, they should serve to illustrate what could be done with fundamental laboratory data if they were extended to cover the field of consolidated sands. From this point of view, it is hoped it will serve to encourage further laboratory research on this problem. The particular application to be treated here relates to the calculation of the productivity factors for oil-gas-water systems in the steady state. This specific problem seems especially appropriate for discussion in view of the recent publication by Johnston1 of the results of produc-

Jan 1, 1942

By C. A. Hartinagel

During 1941, the total production of crude oil in New York state was 5,185,000 bbl. This represents a small increase over the average for the past five years. From 1921, when the annual production of the state amounted to only 988,000 bbl., there was a regular annual increase in production (excepting one or two years) until the 5,000,000-bbl. mark was reached in 1937, After more than 20 years of oil recovery by flooding methods, it was generally believed, until a few months ago, that the rate of production was nearly at its peak and within a few years the fields would experience a gradual decline as the thicker sands became exhausted and the thinner ones could be worked only at increasing costs. As a result of the present emergency, however, unusual efforts are being made, in spite of higher costs of operation, to increase the output of Pennsylvania grade oil, to which the New York product belongs. Since most of any increased production would be obtained by flooding, and since floods travel slowly, no large increase in production can be expected for some months to come. During the first year, 10 or 15 per cent increase could be obtained, but maximum production, an increase of perhaps 40 per cent, could not be expected until some time during the second or third year. In the Allegany fields, which account for two thirds of the state's oil production, 1246 wells, including water-intake wells, were drilled during the year; 390 more than in the preceding year and 590 more than in 1939. It is evident that much of the best oil territory has already been developed. As producers move toward edge properties and thinner sands, returns will be smaller, whereas costs remain the same or, under war conditions, become higher. It is estimated that at least 60 million barrels of oil is in sight and will be produced from the thicker sands by present recovery methods. In the thinner sands and edge properties, some 35 million additional barrels can be produced at a profit only if prices become higher. In view of the fact that there is little hope of finding new oil pools in New York, one of the future problems of the oil producer will be to obtain adequate returns for increased production costs. The year started with a posted price of $2.15 per barrel of crude. There were five successive price increases until the high of the year was reached at $2.98 on Aug. 14. Eight days later the Office of Price Administration directed that the price be reduced to the June level of $2.75 a barrel, which remained in effect to the end of the year. With rising costs of operation, it is feared that many of the smaller properties cannot continue production unless the Federal price cut is revoked. During the year, Allegany Refiners Inc., a local enterprise founded in 1933, with plant at Bolivar, western Allegany County, increased its refining capacity from 1000 to 1500 bbl. daily. At the same time equipment was added to make the plant a complete lubricating-oil refinery, including facilities for the refining of wax into the finished product. Previous to the enlargement, it was necessary to sell the wax

Jan 1, 1942

By Kefton H. Teague

Attempts to locate domestic supplies of sillimanite have been unsuccessful until recently. This paper describes recent discoveries of sil-limonite-bearing schists in the Southeastern States, with emphasis on geology of the deposits, mineral composition, origin, and reserves. Statements concerning possible methods of mining, milling, and utilization of sillimanite are given. Results from refractory tests on a laboratory scale are summarized. SINCE 1917, when synthetic mullite was first used in spark plug porcelains, there has been a continued search for natural sillimanite. During the recent war this search was intensified, not only for sillimanite but also for any materials which could be used satisfactorily as a substitute for the imported kyanite from India. The Indian massive kya-nite does not decrepitate during calcination as does our domestic bladed kyanite, thus a coarse grog can be obtained from it. Some of the most promising domestic materials suited for high temperatures are limited in quantity. Massive topaz from Chesterfield County, S. C., showed promise of possessing desirable refractory properties; but the action of combined fluorine, liberated during calcination, upon equipment and surroundings, as well as a limited supply of ore and the presence of impurities discouraged its use. Residual lumps and boulders of massive kyanite, similar to the material imported from India, occur in Georgia. This material, like the massive topaz, is of limited quantity. Andalusite from California and dumortierite from Nevada are satisfactory high-temperature refractory materials. Their uses have been restricted to specialized products since the location and character of the deposits are such that large production is impractical. Sillimanite, like kyanite and andalusite, has the theoretical chemical composition of Al2SiO5. It has a hardness of 6 to 7; vitreous, silky to subadamantine luster; specific gravity of 3.2 to 3.3; and is gray to bluish gray in color. Under the binocular microscope, the crystals are transparent. The mineral may occur as dense, fibrous mats (fibrolite) composed of fibrous, sometimes radiating hair-like crystals in schist which are associated with igneous intrusions. Deposits of this type have widespread distribution, but none discovered to date appears to have commercial possibilities. Sillimanite also occurs as bundles of crystals disseminated in biotite schist, as noted in the Hart-Elbert-Madison County, Ga., area and in some of the South Carolina and North Carolina deposits. This type of material has been called prismatic sillimanite by the U. S. Bureau of Mines. Deposits of this variety appear to offer commercial possibilities. When heated above 1650°C, sillimanite expands about 6.5 pct and is converted into a mixture of mullite (3Al2O3 . SiO2) and vitreous silica. This is a stable mixture which has a specific gravity of about 3.15. General Geology: Sillimanite (fibrolite) is a mineral common to the pre-Cambrian metasedi-ments of the Southeast. It occurs throughout the crystalline schists which lie between the Fall Line on the southeast and the established Paleozoic rocks on the northwest (fig. 1). In addition to the meta-sediments, this area contains pre-Cambrian igneous

Jan 1, 1951

By C. W. Carpenter, P. T. Bail, J. E. Bobek

This paper presents the results of model studies made to demonstrate the validity of applying the "basic" waterflooding scaling relationships of Rapoport1 to water-wet reservoirs composed of communicating strata of different permeability. Results demonstrate that these relationships can be validly applied, and also show the combined effect of variables on recovery. This demonstration was needed to confirm that the sizable effects of communicating strata on waterflood behavior, observed in model studies, were actually representative of field behavior. INTRODUCTION Rapoport1 Collins2 and others have presented scaling laws for modeling water-oil displacements. The validity of these laws has been experimentally demonstrated for homogeneous systems only. Recently, however, several investigators have presented the results of multilayer model studies made to determine the effects of viscous, capillary and gravitational forces on oil recovery in systems composed of communicating layers of different permeability. Dyes and Braun,3 using miscible displacements to simulate water flooding, showed that vertical communication adversely affects recovery at unfavorable viscosity ratios in the absence of capillarity. Ogandzhanyants and Egorova, 4 Gaucher and Lindley,5 and Richardson and Perkins6 modeled water-oil displacements in layered systems using immiscible fluids with capillary forces present. These investigators found more efficient behavior than in the miscible system of Dyes and Braun. However, since the scaling laws had not been verified for heterogeneous systems prior to or during these tests, it was necessary to assume that the results were representative of field behavior. This report presents the results of model studies made at Jersey Production Research Co. to find out if the waterflooding scaling relationships are valid when applied to water-oil displacements in heterogeneous reservoirs with vertical communication. Data obtained in the study show the combined effects of viscous, capillary and gravitational forces on oil-recovery behavior. The studies were performed in strongly water-wet systems where strong imbibition forces were present. For systems of different wettability, the effects of capillary imbibition would be somewhat different than those presented. APPROACH The scaling laws studied were those developed by Rapoport1 and designated by him as "basic" scaling laws. These relationships require that the model be scaled to the geometry of the prototype, and that the model and prototype be operated at the same viscosity ratio and have identical relative permeability curves, contact angles and boundary conditions. It is also necessary that the groups** be identical in the two systems, although any of the parameters making up the groups may be different. Finally, the capillary pressure of one system must be directly proportional to that of the second. Studies were conducted in two four-layer models, representing quadrants of five-spots, which were geometrically similar and which had the same glass-bead packing. The fluids used assured the same wettability in both models. Thus, the contact angles and relative permeabilities of comparative sand layers in the two models were identical and the capillary pressures were directly proportional. However, one model had a characteristic length three times that of the other. To make the scaling groups equal and to check the scaling laws, it was necessary to adjust the rate, water-viscosity level, interfacial tension and water-oil density difference to compensate for the difference in model sizes.

By W. D. Von Gonten, R. L. Whiting

Regression analysis was used to correlate the physical properties of 478 sandstone and 90 carbonate core samples. Porosity, permeability, electrical formation resistivity factor, capillary pressure and the sonic velocity of the shear and compressional waves were measured. Prediction equations for porosity, permeability and electrical formation resistivity factor were found which should be useful in understanding the relationships between the physical properties of porous media in formation evaluation. INTRODUCTION The physical properties of porous media are important to the petroleum engineer and geologist. To evaluate fully the potential and behavior of a subsurface formation such as a petroleum reservoir, certain physical properties of the porous medium must be known. The problem of accurately determining physical properties of subsurface formations has not been solved because many determinations must be made by indirect measurements and because of the difficulties caused by complex pore structure and presence of clays in most naturally occurring porous media. Due to the difficulty in measuring some of the physical properties of porous media, it would be advantageous to be able to predict a certain physical property of a rock from other physical properties of the rock which could be measured more easily and more accurately. Since most potential reservoir rocks are heterogeneous, relationships between the physical properties are very complex and thus far no satisfactory correlations based on theory or laboratory models have been developed. It appears that empirical relationships obtained by measuring the physical properties of a large number of samples of naturally occurring porous media and applying regression analysis to develop equations for one physical property in terms of other rock properties is the best approach. REVIEW LITERATURE The three physical properties used as dependent variables for correlating purposes were porosity, permeability and formation factor. Since formation factor is more difficult to determine, a brief review of the literature is provided on this property. The first work on determining formation factors was published by Archie1 in 1942. He defined this property of a porous medium as F - Ro/Rw......(1) where Ro is the resistivity of the porous medium when completely saturated with a brine of resistivity Rw. Archie found the best correlation between formation factor and porosity was the following equation, where is the porosity fraction and m is the constant characteristic of the rock. The value of m was 1.3 for unconsolidated sand packs, and ranged from 1.8 to 2.0 for consolidated sandstones. In 1950 Patnode and Wyllie2 and De Witte3 observed that the formation factor as determined by Eq. 1 was valid only when the porous medium contained no conductive solids such as clay or shale. When conductive solids are present the formation factor is also dependent on the resistivity of the saturating fluid. Therefore, in samples containing conductive solids the formation factor decreased as the resistivity of the saturating fluid increased. Because of this. the measured formation factor was called the apparent formation factor and was designated Fa. Patnode and Wyllie proposed the following equation,

By C. G. Dunn

The measurement of interfacial teusions or grain boundary energies in metals is an important metallurgical problem, especially since it bears on growth and nucleation processes. Statistical methods of measuring equilibrium grain boundary angles, which relate interfacial tensions, have been used by some investigators1'2 but more direct methods would be preferred. A direct way, based on a simple extension of a successful method of growing single crystals of silicon ferrite to predetermined orientations in flat specimens,3 is to produce three-grain specimens in such a way that the equilibrium common grain boundary will be perpendicular to the surface of the specimen. The angles to be measured then appear as the grain boundary angles in the surface of the specimen. The method of producing a single crystal specimen with a predetermined orientation is basically the same as that employed by Yoshida and Fuji-wara4 in their work on aluminum wires. The specimen, prior to any single crystal transformation, must have a matrix which will support the growth of a crystal of the desired orientation. Growth may occur through exaggerated grain growth or, if the matrix is strained a critical amount. by normal recrystallization. In either case the matrix must have stability at the temperature used to effect the transformation, this stability appearing as a long induction period for exaggerated grain growth or for the formation of recrystallization nuclei. Additional control is gained by using a high temperature gradient through which the specimen is moved at a suitable rate. To obtain the desired orientation, the specimen is fed a short way into the furnace producing one or more crystals in the hot end. After the specimen is removed from the furnace, the orientation of a crystal is determined, so that this crystal may be reoriented by properly deforming a narrow piece of the matrix between the end crystal and the rest of the specimen. This part of the specimen in the case of silicon ferrite is preferably held at red heat during the reorienting process. Fig 1 shows a specimen which is ready to be transformed into a single crystal through growth of a reoriented "seed" crystal. When the method just described is applied to the production of a three-grain specimen two crystals are grown first side by side in one end, the specimen is then reversed and the third grain grown from the opposite end. A suitable group of grains each of different orientation is one where all three grains have the same crystallo-graphic plane in the plane of the specimen. Fig 2 shows a photograph of a three-grain group prepared as described. The notches are introduced in the open ends of the grain boundaries to anchor them during the final annealing operations which ultimately should bring the grain boundaries to the lowest energy configuration. Two-grain groups with different crystallographic planes in the plane of the specimen can be similarly prepared and treated. If the two grains have different surface (gas to metal) energies per unit area, the equilibrium condition leads to a curved grain boundary.* * This feature of the problem was pointed out by J. c. Fisher. References 1. Cyril Stanley Smith: Grains. Phases and Interfaces: An Interpretation of Microstructure. Trans. AIME 175, 15. Met. Tech. TP 2387, June 1948. 2. D. Harker and E. Parker: Grain Shape and Grain Growth. Trans. A.S.M. (194,5) 34, 156-195. 3. C. G. Dunn, A. Seddon, and R. Wylie: Unpublished Work, 1946-1947. 4. Takeo Fujiwara: A Method of Producing A Long Single-Crystal Wire of Aluminum with any Desired Crystallographic Axis. Jnl. of Sci. Horoshima Univ. A, (1939) 9, No. 3, 227.

Jan 1, 1950

By L. C. Armstrong

Twice in the past two years and in two widely separated localities—ane near Williamsville, Mo., and the other in the Allard Lake district of Quebec— the Contract Drilling Division of the Longyear Company has experienced perplexing difficulties in drilling granitoid igneous rocks. The rocks in both places are characterized by appreciable amounts of feldspar intimately inter-grown with quartz particles of microscopic dimensions. The disappointingly slow rate of advance and the exceptionally high bortz loss, obtaining during the life of these two projects, are ascribed largely to the resistance to abrasion of these two minerals when arranged in this intergrown pattern. Whether all intergrowth-bearing igneous rocks would offer extraordinary resistance to bit progress cannot be stated with assurance on the strength of these experiences alone. More data on diamond drilling this sort of material in a number of localities are needed before any generalizations can be made safely. It should be pointed out that the lack of time and funds made it impossible for the writer, or other persons interested in correlating the details of bit histories with the kinds of rocks drilled, to be present during the performance of the contracts. However, the records kept in the normal course of drilling are deemed complete enough to be reportworthy. This information is presented here together with the findings made in studies of the rocks involved, with the thought that it may attract the comments of others who may have encountered similar refractory drilling conditions. A pooling of knowledge on the problem would be of material aid in devising more efficient cutting tools and procedures for penetrating this kind of rock. Drilling Blastholes in the Williamsville Granite Due to the unsatisfactory perform- ance of pneumatic percussion drills in boring blastholes on a construction contract near Williamsville, Mo., tests were made with a diamond drill. The poor progress achieved and the excessive loss of diamonds, however, soon led to the abandonment of these trials. The diamonds, in all of the bits tried, lost their cutting edges and acquired a polish after being in service for distances ranging from a few inches to a few feet. Coring bits containing surface-set, whole-stone bortz in a tungsten powder matrix were employed. The cost assignable to bortz wear averaged $7.17 per foot. This item of expense is several times the amount normally expended in diamond drilling in firm, unfractured, granitic rocks. Diamond-impregnated, tungsten carbide bits also were used without success. The diamond wear was at the rate of $0.98 per foot, but the diamond chips became too polished for further duty in less than a foot of drilling. The Williamsville granite is pink and medium-grained. In the hand specimen, it has a fresh, sound appearance; it is seemingly composed almost entirely of interlocking grains of feldspar and quartz and has no discernible features suggesting a greater durability than is usually found in rocks with this composition and texture. Microscopic examination, however, reveals a predominance of feldspar grains with more or less regularly distributed and sharply angular masses of quartz (see Fig 1). The pattern assumed by the two minerals in this mode of occurrence is referred to as a "graphic intergrowth," as it bears some resemblance to the cuneiform characters of ancient Persian writing. The other principal constituents are quartz-free feldspars (microcline and orthoclase) and quartz. All of these constituents are in nearly equidimensional grains, ranging up to about 3 mm in length. There are also

Jan 1, 1950

By W. H. Triplett

DISCUSSION John G. Barry (Mexico)—"The Nerinea limestone," writes W. H. Triplett, p. 584, "is ... medium-bedded (0.5 to 1.0 m)...." This is the Zuloaga formation. It has always been described as thick-bedded (1.0 to 3.0 m). "Whether the marls and shales were less amenable to replacement," he goes on to say, ". . . is a matter of opinion." In general, it is probable that the thinner-bedded formations were less competent than the nearby thicker-bedded, so that the latter produced pre-mineral breccias when all were subjected to flexing stresses. With reference to Mr. Triplett's analysis, p. 584, under Lower Cretaceous, in the Taraises and Cupido formations some few horizons should be considered as possibly containing hidden orebodies. In the Potrero camp, shown on the general map in the northwestern part of Fig. 4, p. 587, several mineralized beds are known; they are found throughout the whole thickness of the Cuesta del Cura formation. With regard to intrusive rocks, p. 585, the general map, Fig. 4, shows that the Potrero and Noche Buena camps are near a third, monzonitic intrusive. It seems doubtful that the Aranzazu was any hotter than the Providencia camp. However, the former does contain large deposits of exogenetic silicates, which in large part occur within the Zuloaga limestone, as shown by Bergeats in a stereogram. At the Aranzazti camp the La Caja formation was only slightly changed, whereas it was altered highly at the Providencia, possibly en-dogenetically. That the temperatures at the Providencia camp were relatively high at one time is also shown by the tourmaline veinlets and lenses in the monzonite and by the garnets on Temeroso peak; high temperature mineralization has possibly been eroded. Maps and sections show that the Concepcion del Oro —Temeroso stock occupies the original locus of some 40 kms of sedimentary rocks. The remains of large roof pendants at Carmen and Animas indicate that stoping was active. Whether all the sedimentaries were stoped and assimilated presents a lively problem, a correlative of which would be an estimate of the original constitution of the invading instrusive rock. As to extrusive rocks, see p. 585, there is also a large thick area of the extrusives left near Noche Buena in the "La Caja" intramontane valley of the La Caja range. This place gave its name to the range. The volcanics are also said to occur in considerable amount in the Mazapil valley.'' Turning now to the remarks under Regional Structure, p. 586, as partly indicated on the general map, Fig. 4, the Mazapil Mountains of the Mazapil region are a continuous, U-shaped range including a northern leg of some 24 km, a southern leg of similar length, and a uniting base which lies to the East and which measures some 10 km in a S 20 E direction. Thus the U-shaped mountains are continuous through a length of 58 km and also contain one continuous anticline, the adjacent valleys being synclinal. The northern leg of the U is called the La Caja range, the base is called the Concepcion del Oro range, and the southern leg the Santa Rosa range. The ranges in northeastern Zacatecas and southern Coahuila contain anticlines and the valleys contain synclines, which where thin are necessarily highly compressed isoclines with very steep dips. Many of the anticlines also have isoclinal components which are overturned, original mushroom tops being indicated. The anticline in the base of the U of the Mazapil Region, Concepcion del Oro range, is a recumbent anticline, over to the ENE, with a necessarily subjacent recumbent syncline.

Jan 1, 1953