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By J. J. Gilvarry, B. H. Bergstorm

The first part of this paper describes a new approach to the problem of energy relationships in fracture and comminution. The basic theoretical method used (as contrasted to previous empirical or semi-empirical approaches) is an attempt to verify or disprove the hypothesis of von Rittinger, In the second part of the paper, theoretical conclusions for the three headings of single fracture, plural fracture, and comminution are tested. Agreement between theory and experimental results is demonstrated. The classical hypotheses on the energy relationship in brittle fracture are those of von Rittinger-that the energy required is proportional to the new surface formed— and the alternative one of Kick.' Over the years, repeated attempts have been made to discriminate experimentally between the two assumptions, or to replace both of them, as has been done by Bond? However, no semblance of agreement seems to exist among different investigators. This paper is the first in a series essaying a new approach to the entire problem of energy relationships in fracture and comminution. The purpose of this program of research is to verify (or disprove) the hypothesis of von Rittinger. In contrast to previous empirical or semi-empirical approaches to the problem, the basic method adopted is theoretical. The prime aim is to determine the distribution function for fragment size theoretically and to verify the predicted distribution experimentally. This approach should make possible determination of the total surface of the particles by integration over the corresponding distribution function; one may hope that this direct procedure will yield more definitive results than use of gas adsorption or other methods. The surface area so obtained can then be compared with experimental energies, as obtained by Bergstrom, Sollenberger, and Mitchell,4 for example. It is convenient to distinguish between single fratture, plural fracture, and comminution. Single fracture of a brittle solid is defined as fracture by an external stress system which is removed instantly and permanently when fracture is initiated. Plural fracture consists of single fracture of the original specimen, followed by a sequence of only a few secondary fractures; comminution differs in that the sequence of secondary fractures consists of a large number of repetitive steps. For single fracture, Gilvarrys has given a rigorous derivation of the proper distribution function for fragment size, based on a closely defined physical model and deduced strictly by the laws of probability. Gilvarry and Bergstrome have compared the predictions of the theory with experiment, and have found excellent agreement. The prior work of Gilvarry and of Gilvarry and Bergstrom considers only single and plural fracture. The purpose of the present paper is to extend the discussion to the case of comminution. For prefatory purposes, the theory of Gilvarry for single fracture will be outlined. The considerations will then be applied to the cases of plural fracture and comminution. SINGLE FRACTURE The derivation is based on the Poisson law.7 For Points distributed with mean density y over a domain, this law states that the probability p(t)dt of one point lying in the range t to t + dt with none in the interval 0 to Ms p(t)dt = ye-yt dt. For this distribution to be valid, it is necessary and sufficient that the points be distributed at random, individually and collectively in the sense of ~~~.7 The former qualification requires that the position of One Point be independent of another, and the latter implies that the probability of a region containing a

Jan 1, 1961

By James J. Wise

INTRODUCTION One basic design feature utilized in all caving and sublevel stoping techniques is the drawpoint. These draw- points may be located on sublevels when using sublevel caving methods, or may be located at the floor pillar when using block caving, sublevel stoping, or vertical crater retreat methods. How the drawpoint is designed and developed, how the ore is withdrawn from it, and how the ore is hauled to the shaft or portal encompasses the loading and hauling function. Historically, predominate loading and hauling equipment for caving and sublevel stoping has been scraper slushes, air powered overshot loaders, and rail mounted train haulage. All of this equipment has two common constraints. 1. The equipment locked into specific work sites and is not easily shifted to another work site. This constraint can often lead to low utilization and low productivity of the equipment. 2. The equipment is designed to work in the horizontal plane, which requires that the various horizontally-oriented working levels be connected by vertical raises. Vertical development by means of raises is not only increasingly expensive, but also is not well adapted to movement of large equipment into the s topes. In the last 20 years, two revolutionary labor saving concepts have become common in caving and sublevel stoping. 1. Long-hole drilling, which has mechanized the development of the drawpoint extraction structures as well as the actual stoping and undercutting. 2. Vertical access by means of trackless ramps between levels, and the consequent use of rubber-tired vehicles not only for loading and hauling ore, but also for the rapid movement of men, material, and equipment into the stopes. The introduction of trackless mining systems for loading and hauling has not been easy. Mine planners have had to re-orient their thinking to the larger operating space required by trackless equipment. Larger access drifts have necessitated reconsideration of mine layouts to insure proper ground support. Spiral ramp developments were often laid out on slopes steeper than the equipment could negotiate economically. Mine operators had to accept the added responsibility of roadway maintenance, water removal, increased ventilation, and more technical mechanical maintenance. As the mine operators enthusiastically embraced the superior productivity of trackless mining systems, they some- times disregarded opportunities to combine the older types of equipment with trackless vehicles to maximize productivity at lowest cost. In order to gain a proper perspective on this problem, it is necessary to review the various techniques of loading and hauling and to become more aware of the advantages or disadvantages that each system or combination contributes. LOADING Loading consists of two functions, (1) primary loading from a drawpoint and (2) secondary loading into long- haul system, a truck, train, or possibly a belt conveyor. Mine planners have four basic loading systems available to fit various operating conditions. These are, (1) gravity, (2) scrapers, (3) rail-mounted loaders, and (4) trackless loaders. Each system can produce optimum results under specific conditions. Gravity Loading Gravity loading is probably the oldest system in general use today.

Jan 1, 1981

By John Blatchford, H. O. Hofman

The leading antimony mineral is stibnite. In smelting stibnite ore two processes are available, precipitation and roasting-reduction. The former is suited only for high-grade ores. As low-grade ores are more common than high-grade, roasting-reduction is of greater importance than precipitation. In the roasting process the aim may be to leave the oxidized antimony in the ore, or it may be to volatilize as much of the antimony as possible, collect the volatilized oxide as a rich intermediary product and smelt it for antimony, leaving the gangue poor enough to be considered a waste product. Whichever way the roast is conducted certain difficulties inherent in stibnite are encountered. These are: 1. The low melting point of stibnite which, according to Pélabon,' is 550°C., according to Wagemann2 540°C., and according to Borgstroma 546°C. 2. The ignition temperature: According to Friedrich,4 stibnite, if heated in air, begins to oxidize at 290°C. if the size of a grain is 0.1 mm. in diameter; at 343", if 0.1 to 0.2 mm.; and 430" if 0.2 mm. 3. The fusibility of a mixture of Sb2S33 and Sb203 which in the form of kermesite (Sb2S3)z.Sbz03 melts at 517°C.6 4. The volatility of Sb2Ss and SbzOs, for which no numerical data appear to exist, although practical experience has shown that they are volatile at low temperatures. As regards the oxidation of metallic antimony, we have the experimental evidence of C. F. Plattner6 that when fused and brought to a red heat, it burns with a bluish-white flame to Sb2Oa which passes off as a

Jan 1, 1916

By L. S. Darken

In the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be represented satisfactorily by the simple equilibrium expression where (P) denotes the concentration of a product and (R) the concentration of a reactant in the reaction r1R1 + r2R2 + • • • D P lP1 + P 2P2 + • • • Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a component is not proportional to its true mol fraction. But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple components and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satisfactorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature— as ionization or the occurrence of polar and nonpolar molecules—are presumably less effective in inetal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By L. S. Darken

In the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be represented satisfactorily by the simple equilibrium expression where (P) denotes the concentration of a product and (R) the concentration of a reactant in the reaction r1R1 + r2R2 + • • • D P lP1 + P 2P2 + • • • Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a component is not proportional to its true mol fraction. But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple components and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satisfactorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature— as ionization or the occurrence of polar and nonpolar molecules—are presumably less effective in inetal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By John T. Norton, V.G. Mooradian

The diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystal-lographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working may be responsible for the increased diffusion rate. The plastic deformation causes a distortion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-torted lattice. On the other hand, it may be that the cold-working causes an increase in surface of contact between the two metals through fragmentation or provides a more intimate contact that is necessary for diffusion. If it is true that lattice distortion is an important factor in diffusion, it seems as if there should be some particular relation between

Jan 1, 1935

By V. G. Mooradian, John T. Norton

The diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystal-lographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working may be responsible for the increased diffusion rate. The plastic deformation causes a distortion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-torted lattice. On the other hand, it may be that the cold-working causes an increase in surface of contact between the two metals through fragmentation or provides a more intimate contact that is necessary for diffusion. If it is true that lattice distortion is an important factor in diffusion, it seems as if there should be some particular relation between

Jan 1, 1935

By Noah Fields Drake

During July and August, 1899, the writer took advantage of an opportunity of going to Shansi to gather some information concerning the geology and value of the already famous coalfields of that province. The long journey, mainly on slow river-boats, and the limited time at command, allowed only about ten days of work to be done in the coal-fields around Tsê Chou. The geologic structure and the rock-formations were found to be simple and quite regular, so that in that time the accompanying sketch-map (Pig. 1) was made, and a fairly good idea of the distribution of the coal and general geologic features was obtained. The map was made by measuring a base-line about three-quarters of a mile long, triangulating for principal points over the field, and filling in the details by rapid sketches. The few elevations marked on the map were taken with an aneroid barometer. Only a few of the great number of towns and villages that are within this densely populated area are shown; and the coal-mines indicated are not the only ones within the area, but the ones where most of the following information about the coal was obtained. The value of this coal-field was first clearly set before the scientific and commercial world by Baron von Richthofen,* who made a geologic reconnaissance of Shansi in 1870. Since that time the hostile attitude of the Chinese government and people towards foreigners and their enterprises has kept the coal-fields from being developed. But the last few years of rapid change in the conditions of China have at last apparently opened a way for the exploitation of this coal-field. The Peking syndicate, a joint English-Italian company, now has concessions from

Jan 1, 1901

By C. H. Jr. Herty

The results of a study of the open-hearth process from the physicochemical view-point are given. This study includes experimentation in small laboratory furnaces and in standard 100-ton furnaces. The behavior of manganese, carbon, and phosphorus are quantitatively explained. The action of "residual" manganese is discussed with reference to its relation to iron oxide dissolved in the metal. The solubility of CO in steel and its relation to dissolved FeO and carbon is given. The equation for phosphorus elimination has been tested out on a 200-ton furnace and the results are given in the text. THE effect of temperature and slag composition on the elimination of metalloids in the basic open-hearth process has been qualitatively understood since the early days of steel making. The quantitative effect has, however, only recently been brought to attention. The effect of slag composition has received more attention than that of temperature, primarily because the range of finishing temperatures in the basic open-hearth process is small compared to the large variations found in the composition of the slag at different periods during the process, and to the variations occurring with the use of raw materials of different degrees of impurity. The effect of slag composition on the elimination of metalloids has been studied by Styri1 from the thermochemical standpoint. This method is open to serious errors, in that thermochemical data at 2900° F. are very inaccurate and in many cases completely lacking. Feild2 has calculated equilibrium constants from the rate at which the metalloids are eliminated. The effect of slag viscosity on rate of elimination will affect the constants calculated by this method. Whitely,3 Colcough4 and others have used slag compositions as the basis for calculation of constants by which the extent of elimination may be calculated.

Jan 2, 1926

By L. Adler

A relatively simple and effective technique is proposed to deal with the failure of geologic masses containing weakness planes. This technique, termed irextended" rupture envelope, provides a means to clearly distinguish rock and soil from fractured rock and, on a theoretical level, considers a matrix-inclusion system. It may also constitute the link between Mohr's and Griffith's failure theories. Included in the article are five sample problems concerning site location, structural design, strengthening the plane of weakness, changing the magnitudes of major and minor principal stresses and changing the orientations of major and minor principal stresses. Engineers trying to solve design problems in rock and soil mechanics have often assumed an iso-tropic and homogeneous medium. For naturally occurring geologic masses this assumption has always been viewed with regret. The following analysis which deals with the effects of plane anisotropy on failure presents a solution to this. The planes of weakness are joints, faults, bedding planes, fracture and cleavage (natural and induced), foliation and schistosity. The physical properties of these weakness planes include an undulating surface, frictional resistance, discontinuous extent, filling material, tightness and presence of water to cause a hydrostatic pore pressure. All of these properties relating to failure can be summarized in Mohr's rupture envelope for the plane of weakness. This, along with the geometrical orientation, strike and dip, of the plane of weakness produces what is termed an irextended" rupture envelope. MOHR'S STRESS CIRCLE AND RUPTURE ENVELOPE The significant features of these concepts are listed below.' 1) A point on the u - r coordinate plane represents the normal and tangential stress components on a reference area in the material. This area can have any orientation. (Fig. la)

Jan 1, 1963

ANDES, lying south of Chuquicamata and north of Braden on the western slope of Chile's cordillera, can best be described as a big well-managed copper-mining enterprise without any peculiarly outstanding features. In point of copper produced, since output started in 1927, it ranks fifth among the Porphyries, being exceeded only by its two Chilean contemporaries and by Utah Copper and Morenci in the United States. Even so, there is little to distinguish it from other properties. It does not have the phenomenally rich ore (better than 2 per cent copper) that characterizes Braden; and it is not in the same class as Chuquicamata whose ore has the excellent tenor of around 1.7 per cent, nor has it Chuqui's immense tonnage of proven ore reserves and potential ore resources. One might say the operations are standard in that there are no basic or radical departures from established practice. A letter from New York supplying me with sundry pertinent facts for which I had asked, makes this comment regarding the answer to one inquiry: "omitted because it is the ordinary equipment found in any well-run mine." The substance of that remark applies generally to the other operations, plants, and facilities. One interesting fact that helps explain this situation should not be overlooked. Until the "new" Morenci in 1942, Andes was the last of the Porphyry copper mines to come into production. It did not do much pioneering because other companies had, of necessity, charted the way in many particulars. The company was organized by the Anaconda Copper interests in 1916 to take over a, group of claims held under option by William Braden who, a few years earlier, had interested

Jan 1, 1957

By A. J. Weinig

The Liberty Bell cyanide precipitate is unique in that it is apt to vary widely in composition in the course of very short periods of time, and a method of refining and melting that would prove highly satisfactory at one cleanup would yield7almost a hopeless "mess" at a second. Table I gives a general conception of the wide range in grade and composition of those raw precipitates. It is evident that no one standard flux could be expected to produce a high-grade bullion with such a widely variable precipitate, and that any method of treatment with acid requires most careful consideration. Refining by Acids Naturally, our first efforts to improve our precipitates were directed along the lines of acid treatment. Table II embodies the results of careful sampling and analysis of one cleanup at the time when wet refining reached its maximum development at this mill. We have now discarded all methods of wet refining, successfully replacing them by a more scientific method of flux calculation described herein, but it is believed that a general description of this wet refining is warranted as it throws some interesting side lights on acid refining in general. Table I.—Range of Composition of Raw Precipitates Per Cent. Gold and silver.................................... 25.0 to 75 Zinc.............................................. 18.0to 30 Lead............................................. 0.5 to 52 Copper........................................... 0.5 to 20 Silica............................................ 1.0 to 5 Calcium oxide...................................... 4.0 to 8 Sulphur.......................................... 0.5 to 8 Column A gives the analysis of the raw precipitate; column B, that of the precipitate after heating with steam, with frequent addition of hydrochloric acid until a point was reached where the batch had a strong tend-

Jan 1, 1917

By D. Grosse

At the beginning of the 1960's, the Hannoversche Portland-Cementfabrik A. G. needed to open a new quarry. The land on which this quarry was to be developed was completely flat and separated from the existing quarry by a navigable canal. The area had been exploration-drilled previously, so that enough reliable data on the chemical properties of the deposit were available. From the geologic point of view, the deposit under a very moist surface belongs to the Turon (Upper Chalk) formation, soft on the surface and medium to very hard farther down. Between the 15% sloping banks of chalk (with a calcium carbonate content of 75 to 90% and running from west to east), there are numerous beds, up to 3 m deep, which are rich in alumina and iron oxide but contain only 50 to 60% CaCO3. In the old quarry-worked conventionally by deep-hole drilling, a 2-cu-m shovel, and 900-mm track with 6-cu-m dump cars-an adequate and modern crushing plant was available. The plant crushed the moist material (11 to 13% H2O content) down to 0 to 50 mm. INSTALLATION OF ORIGINAL MOBILE CRUSHER It was decided to employ a mobile crushing unit in the new quarry; the moist and soft ground did not permit the use of heavy trucks for transporting the material, and a road network would have entailed a large investment. The use of a rail system was eliminated from the beginning, since the ground would be very uneven after the quarry was developed. At that time only one prototype of a crawler-mounted mobile crushing unit existed. This unit was operating in a nearby works as a primary crusher. A similar, slightly improved machine (Fig. 1) was purchased

Jan 1, 1969

Data about production are very meager. In this county from the earliest days until after the Civil War, the amount of coal used locally greatly exceeded that shipped on account of the iron produced; for many years the furnaces used raw coal for melting the ore. In 1846 it was stated that in this county one ton of iron required three tons of iron ore and three tons of local coal used raw.1 In 1864, eleven furnaces in Pennsylvania using 102,230 tons of raw coal produced 44,671 tons of iron, or 2.3 tons raw coal per ton of pig iron .2 This was probably as good a record as was made, as nearly all furnaces changed to coke some years later. Neither of these figures include the coal used for steam and other purposes around an iron plant. The Beaver and Erie Canal was opened in 1845 and the shipments shown from then to 1865, inclusive, are of coal received by the canal at Erie, and do not include any used at local points along the canal. From the completion of the Erie and Pittsburgh Railroad in 1864 the tonnage shipped by canal decreased. rapidly, and, while the canal shipments after 1864 are supposed to be those received at Erie by canal only, they may include some rail tonnages. Tonnages on Erie and Pittsburgh Railroad may, and probably do, include some used locally; those on the Jamestown & Franklin Railroad do not. It is likely that both canal and Erie and Pittsburgh Railroad figures include some coal originating in Lawrence County, and possibly a little from Beaver County. These tonnages are not duplicated in the data for either of the other counties. Not all of the railroad reports can be found now.

Jan 1, 1942

By J. L. LeBlanc, R. L. Lewis

This study presents an analysis of annular backpressure variations associated with controlled gas kicks and their pronounced effect on casing .strings and exposed under lying formations. A mathematical model describing the volumetric behavior of an extraneous gas as it is transported from reservoir to .surface conditions under changing temperatures and pressures has been programmed in a Kingston FORTRAN II language for digital computer analysis. The gases under investigation typify Gulf Coast reservoir gases within a 0.6 to 0.7 .specific gravity range. The program output has been substantiated by actual field cases. of gas kicks encountered in Gulf Coart we1l.s. The development of empirical equations for calculating suitable gamy deviation factors for unique temperatures and pressures was incorporated in the program to provide realistic solution.. An output listing of annular backpressures and corresponding equivalent fluid densities resulting at a predetermined critical depth (casing setting depth) and total depth for selected .stages of circulation is provided in a chronological .sequence. Additional information including reservoir pressure and temperature, kill rnrid density, produced gas or surface volume of the expanded gas intro vion, drill pipe and annular volumes can he obtained from the model. This paper illustrates that a precise knowledge of the volumetric behavior of extraneous gases in annular flow and its effect on equivalent fluid densities at a critical depth is significant and should receive .serious consideration in controlling threatened blowouts and in the design of drilling programs. Surface pressures in excess of formation limitations are a threat to zones of lost circula/ion and are potentially injurious to productive intervals. A knowledge of annular backpressure and equivalent fluid density profiles for probable gas kicks aids in a technological accomplishment of drilling programs and provides a .sale tolerance in the event a threatened blowout is encountered. Introduction Drilling operations are frequently interrupted when the drill bit penetrates permeable gas sands with reservoir CtfuJ manuscript was received in Society of Petroleum Engineers ofice Am. 1 1967. Revised manuscript received JuIy 7. 1968. Paper (SPE 1860) kae presented at SPE 42nd Annual Fall Meeting held in Houston. Tex., Oct 1-4, 1967. @ Copyright 1968 American Institute of Mining, Metallurgical, and Petroleum Engineem, Inc. pressures greater than that exerted by the drilling fluid. The differential pressures resulting permit an extraneous influx of gas into the wellbore. A suspension in drilling progress is necessary to restore fluid equilibrium throughout the system. Whether formation gas kicks originate unintentionally or by design, the prospect of a threatened or actual blowout exists and a method assuring a safe and effective well control procedure must be observed. A significant contribution to well control technology was advanced by Records et a1.l in 1962. Using the concept of transmitting a constant equivalent formation pressure at the point of intrusion, Records et al. introduced a calculation technique providing the annular backpressures encountered in a well control environment as a func tion of the volumetric behavior of a 0.6 specific gravity natural gas. In essence, the procedure outlined an annular backpressure schedule in terms of fluid volume circulated at different stages of a well control operation. A number of other publications2-' proposing various techniques for controlling gas intrusions in a wellbore achieve pressure control essentially through maintenance of a constant bottom-hole pressure by surface choke adjustments. The subsequent pressure effects induced in the annulus unfortunately receive little emphasis. Due to the tedious and repetitive nature of annular backpressure computations, a theoretical solution by digital computer is introduced for predicting annular backpressure and equivalent fluid density profiles associated with controlled gas kicks. We point out the effects of volumetric behavior of extraneous gases in annular flow and related field phenomena on equivalent fluid densities at a critical depth. The investigation indicated that equivalent fluid densities at a critical depth are of significance and should receive consideration in the control of threatened blowouts and in the design of drilling programs. Theoretical Considerations The mechanism of vertical gas flow through an annulus is governed by the PVT properties of the fluid, the pressure distribution within the system, the fluid flow rates and the geometry of flow. Due to the numerous variables involved in this type of problem, certain assumptions were imposed in deriving the mathematical model and in establishing the solutions. Two gases, characterized by specific gravities of 0.6 and 0.7, were selected to typify Gulf Coast reservoir fluids. The gas intrustion entered the wellbore as an immiscible 'References given at end of paper. JOURNAL OF PETROLEUM TECHNOLOGY

Jan 1, 1969

By A. H. Larson, R. J. McClincy

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke' first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer' who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier' gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970

By Edwin F. Nelson, Charles Wirth, Gustav Egloff, C. D. Maxutov

The treatment of emulsified crude oils has been a problem for years in the petroleum industry. Until comparatively recently various methods of settling with and without chemicals have been used with indifferent success. Since wells have been acidized, emulsified crudes have been produced, which add considerably to the need for improved methods of treatment. The presence of large quantities of salts in the oils from acidized wells has presented several new problems to the industry. The use of hydrochloric acid in well treatments has caused the formation of sodium, magnesium, and calcium chlorides by interaction with the dolomitic limestones. These salts dissolve readily in the water normally present in the oil, and they are therefore incorporated in the emulsified oil. The crystalline salts have also been found in the oil, prevented from settling by protective films such as asphalt, resins and petrolatum. In some instances, free hydrochloric acid has been found. The salts may be present in crude oil in amounts ranging from a few pounds to over 1000 lb. per 1000 bbl. of oil. The transportation of these crude oils through pipe lines has led to erosive and corrosive effects, which are a tremendous cost to the petroleum industry. During 1937, more than 1,200,000,000 bbl. of crude oil was transported through pipe lines. Of this quantity approximately 10,000,-000 bbl. was water, and considerably more than 50,000,000 lb. was salts. If the crude oils were treated at the producing wells to remove the salts and water, an appreciable saving would be possible. The treatment would not be difficult, since it has been found that these oils are more easily treated at the time they are produced than after the aging and more stable emulsification that occur before they reach the refinery. Since great costs are involved in the use of these salty crudes at the refinery, treated oils essentially free of salts would naturally command a premium. The real added costs lie in refining salt-containing crude oils. Severe corrosion of refinery equipment in both topping and cracking installations has appeared in many refineries. Chemicals such as ammonia, lime and

Jan 1, 1938

By S. Shapiro, G. Krauss

We will reply to Dr. Pitsch's discussion by 1) presenting in greater detail the single surface trace analysis which we performed on the reversed austenite plates in a single parent plate of martensite of known orientation, 2) relating the results of our analysis to the conclusions which Dr. Pitsch makes on the basis of our data, and 3) examining the validity of our selection of twenty-nine individual traces from the over 200 austenite plates which were observed in a surface of this single martensite plate. Fig. 7 shows a standard (001) projection of the martensite plate from which the austenite-martensite interface traces were taken. The traces are plotted on the projection as the small solid circles, and the great circles corresponding to the loci of plane normals which could contain each trace or could intersect the surface plane along the measured directions are also plotted. It can be seen that these great circles intersect at a point which corresponds to the normal of the surface plane on which the traces were observed. Also rate which occurred only at particularly low heating rates, see Figs. 1 and 3 in the paper.2 Since in this case the interpretation of Jana and Wayman is plausible and since we have no alternative to this interpretation, we would like to state only that the existence of a diffusion-controlled reversal at low temperatures seems to be not yet proved beyond any doubt. The author wishes to thank Professor G. Krauss for making available his manuscript prior to publication. It is also a pleasure to acknowledge the lively written discussions, which the author has had with Professors G. Krauss and C. M. Wayman prior to this communication. The financial support of the Deutsche For-schungsgemeinschaft for the work on which this communication is based is also gratefully acknowledged. plotted within small dotted circles which represent a i3 deg scatter in each of the twenty-four unit stereo-graphic triangles are our A and B poles7 and the pole P determined by Kessler and itsch.' The data presented in Fig. 7 permit a direct association of the measured traces and the various proposed habit plane poles for the reversed austenite plates in the martensite crystal. If the sample measurements do in fact

Jan 1, 1969

By R. L. Stone

None of the currently used methods of testing bentonites as binders for strengthening iron ore pellets is entirely adequate by itself. Since more knowledge was needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced, attention was paid to possible new techniques for rating bentonites. With the structural nature of bentonites — in particular, the montmorillonite component — the possibility of rating bentonites on the basis of zeta potential was investigated. These bentonites were also rated by conventional tests and measurements, including colloid content, barrel yield, pH, chemical analysis and physical tests on green and dry pellets. A mechanism for pellet bonding based on electro-kinetic forces between the bentonite and the iron ore concentrate appears to be feasible. In pelletizing, from 6 to 18 lbs of bentonite is added per ton of concentrate to give strength to the green and dry pellets. In some operations even more bentonite than is required for strengthening purposes must be added for moisture adsorption to pennit balling of the concentrate. Since bentonite is thus a major item in pelletizing, more knowledge about the way in which bentonites act as binders and better ways of rating this ability would help in the difficult job of selecting the right bentonite for a given concentrate. The fact of the matter is that although several methods are in current use for testing bentonites, none of these methods are consistently foolproof. For example, a given bentonite may rate high by several standard tests yet turn out to be a poor binder, and of course the reverse also occurs. Actually, more knowledge is needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced. In this study attention is therefore paid to possible new techniques for rating bentonites. With the structural nature of bentonites as a starting point, we investigated the possibility of rating bentonites on the basis of the zeta potential, i.e., the electrokinetic ootential on the montmorillonite colloids — the main component of bentonite binders. The zeta potential technique was applied to a range of commercial bentonites from several areas in the U.S. and abroad. These bentonites were also rated by conventional tests and measurements, including:

Jan 1, 1968

By C. Edwin Nighman

THE following is a description of the methods used in rescuing men and extinguishing the underground fire at the Pennsylvania mine, Butte, Mont. This fire, which cost the lives of 21 men, began about 9 p.m., Feb. 14, 1916, at or near a ventilating fan on the 1,200 air-shaft station. This shaft at that time was downcast, while the main hoisting shaft was upcast. Owing to the proximity of the fire to the air shaft, the air in the latter soon became heated, and as the fan on the level was not running¬the power having been cut off shortly after the outbreak' of the fire-the aim' shaft became upcast to the 300 level. At this point a blanket of cold air from the surface caused the smoke and gases to he drawn in on that level and carried down again through the workings to the 1,200. A short time after the discovery of the fire, water was turned down the air shaft through a series of pipes around the collar of the shaft, which caused the smoke to recede, below the 300, so that within 2 hr. it was possible to search that level for the missing men. From the above it will be apparent why the air shaft was upcast instead of downcast as under normal conditions, and why men were suffocated at considerable distances from the seat of the fire. The smoke and gases that came up the main hoisting shaft did not diffuse through the workings to any extent. There are doors on all levels in the connections to the main hoisting and air shafts, but-in the confusion and running around many of these doors were left open, and this undoubtedly caused the smoke and gases to spread more rapidly than they would otherwise have done. It was necessary for most of the men on the various levels to pass close to the air shaft in going to the hoisting shaft, and when they encountered the smoke and gases in that vicinity a number turned hack and climbed down with the direction of the air currents and were then suffocated, while all those who passed through the relatively short pall of smoke to the main shaft were saved.

Jan 2, 1917