Search Documents

By M. H. Merriss

Some years ago, at the plant of the Baltimore Copper Smelting & Rolling Co., the receipt of large quantities of copper blister running high in lead, nickel, and arsenic resulted in the formation of a great amount of very foul slag, in the anode furnaces. A typical analysis of this slag was: Gold, oz. per ton......... 0.09 Arsenic, per cent.......... 0.60 Silver, oz. per ton......'.. 13.20 Antimony, per cent........ 0.50 Copper, per cent......... 19.50 Silica, per cent............ 28.30 Lead, per cent........... 11.90 FeO, per cent............. 19.20 Nickel, per cent.......... 4.60 CaO, per cent............. 1.60 The problem was to get out the copper in marketable form, to save the gold, silver, and particularly the nickel, and to get rid of as much as possible of the lead, arsenic, and other elements that were valueless to the Baltimore plant. In a copper refinery that does not take custom material for matte smelting, the usual method is to smelt the anode slag with coke in a reducing furnace, the black copper thus formed being sent back to the anode furnaces; this was the custom at Baltimore. An average anode slag will contain, perhaps, 40 per cent. copper and such small quantities of lead, nickel, etc., that smelting will get rid of most of these impurities in the black-copper furnace slag. To treat such an impure slag in this way, however, would result in a large nickel loss, and would send back to the anode furnaces all the lead and nickel not so lost, where it would be slagged off again and returned to the black-copper furnace as a slag still more concentrated in impurities. The result would probably be a constantly increasing amount of anode slag containing a likewise constantly increasing percentage of impurities. To avoid such a disastrous closed circuit some other process had to be devised. A small multiple-tank room, built for impure copper as an adjunct to the main series electrolytic refinery, was available, so the following standard process was suggested:

Jan 1, 1924

By Paul Bechtner

THE name bentonite formerly was applied solely to a peculiar clay occurring in Wyoming and South Dakota, which was distinguished from other clays by its unctuous feel when wet and the property of swelling in water. In the last decade scientific studies of clay have recognized that bentonite is composed mainly of the clay mineral montmorillonite and the name bentonite has been extended to cover the entire family of clays that have montmorillonite as their chief constituent. Montmorillonite has the chemical formula of A1203-4Si0-xH2O, With Fe203 and MgO replacing part of the A1203. The montmorillonite crystal is an Si-Al-Si clay mineral, being formed of two silicon-oxygen sheets with an aluminum-oxygen sheet sandwiched between them. In contrast, kaolinite-the chief clay mineral of most clays other than bentonite-is Si-Al, one silica and one alumina sheet. The unit crystal of montmorillonite is much thinner than that of kaolinite, with greater surface area. These differences in crystal structure patterns are leading factors in the dissimilar properties and commercial uses of bentonite compared with other clays. Mineralogically, bentonites are 85 to 90 pct montmorillonite with fragments of feldspar, gypsum, calcium carbonate, quartz and traces of other minerals. They vary in color; the widely used Wyoming type is creamy white when dry and a light shade of tan when wet; the low-swelling bentonites of the southern United States and elsewhere are found in many shades of gray, blue, yellow, red, and brown. Pure white bentonites are rarer and generally of the medium or low-swelling type, though there are a few exceptions to that general rule. PROPERTIES Bentonites may be divided into two general classes: (1) those that adsorb large quantities of water, "swelling" greatly in the process, and that remain in suspension in thin water dispersions; (2) those that adsorb only slightly more water than ordinary plastic clays or fuller's earths, do not swell noticeably, and settle rapidly in thin water dispersions. Another distinction is that some varieties of the No. 2 type

Jan 1, 1949

By S. C. Das. Gupta, B. S. Lement

isothermal formation of martensite occurs in the range of —65o to —197oC and is always preceded by some athermal transformation. By rapid cooling the isothermal, but not the athermal, component of transformation can be suppressed. Stabilization against isothermal transformation can be induced by cycling from below M. to room temperature. A LTHOUGH the transformation of austenite to XV martensite is generally believed to occur only on cooling, recent evidence indicates that this reaction can also occur at constant temperature. Isothermal formation of martensite was observed in tool steel by Fletcher, Averbach, and Cohen.'. They found that the hardening reaction that occurs during the quenching of a plain carbon or low carbon alloy tool steel does not stop immediately when room temperature is reached; instead austenite continues S. C. DAS GUPTA is Research Fellow, Department of Metallurgy, University of Notre Dame, Notre Dame, Ind. B. S. LEMENT, Associate Member AIME, is on the Research Staff, Department of Metallurgy, Massachusetts Institute of Technology, Cambridge, Mass. Discussion on this paper, TP 3123E, may be sent, 2 copies, to AIME by Dec. 1, 1951. Manuscript, April 16, 1951. Detroit Meeting, October 1951. This paper represents part of a thesis by S. C. Das Gupta submitted in partial fulfillment of requirements for the degree of Doctor of Philosophy in Metallurgy to the University of Notre Dame. to transform at room temperature although at a decreasing rate. Since only a small amount of austenite transforms in this fashion, isothermal formation of martensite was considered to be merely a "tailing off" effect of the main hardening reaction. Another point of view was advanced by Kurd-jumov and Maksimova"' * who reported that the austenite-martensite reaction could be suppressed by rapid cooling of a 6 pct Mn-0.6 pct C steel in liquid nitrogen and that as much as 25 pct martensite could be formed by reheating to and holding at subzero temperatures above that of liquid nitrogen. These investigators came to the conclusion that martensite is thermally nucleated at certain special regions in the austenite and subsequently grows to observable dimensions. Isothermal transformation of austenite to martensite was cited by Fisher, Hollomon, and Turnbull" as evidence supporting another nucleation and growth theory of martensite formation. According

Jan 1, 1952

INTRODUCTION Porphyry copper deposits have been reported from the Caribbean area by Pease (1966), Cox, et al. (1973), Guild (1974), Kesler, et al. (1975), and others. This chapter summarizes the most widely known characteristics of those deposits. Only one deposit that conceivably can be classed as a porphyry copper occurrence is in production (Pueblo Viejo, Dominican Republic), but others are known whose tonnage and grade are of economic interest. Deposits in this province may be classified as copper-gold or copper-molybdenum types (Kesler, 1972), but deposits associated with quartz-rich plutons that have high Na2O:K2O and high gold:copper but low molybdenum: copper ratios dominate. Porphyry copper occurrences are reported in the literature from Puerto Rico, Haiti, the Dominican Republic, Jamaica, and Cuba. Only the porphyry copper deposits from Puerto Rico are extensively described in the literature; consequently the Caribbean porphyry copper province in general is not as well documented as the southern Cordilleran orogen. Because past published technical descriptions are incomplete, some data presented here are new to the literature. The Caribbean includes the island arcs between North and South America. Porphyry copper occurrences are known from the Greater Antilles, the generally east-west trending group of islands that lies south of North America. Fig. 48, therefore, only covers the Greater Antilles portion of the Caribbean. Porphyry copper deposits in this area are not described by the Lowell and Guilbert (1970) model in details of metallization (general paucity of molybdenum), alteration (scarcity of orthoclase), or petrography (preponderance of quartz diorite). Therefore, this model should be modified to include deposits associated with quartz-bearing plutons such as those found in the Caribbean. In the Meme deposit on Haiti ore occurs in skarn adjacent to the quartz diorite phase of a composite quartz monzonite-granodio-rite-quartz diorite pluton (Kesler, 1968). This deposit, with a K-Ar 66 m.y. date, is not included in Fig. 48 as a porphyry copper deposit because metallization is restricted largely to the intruded rocks. Although the intrusive rocks at the Meme deposit may contain sulfide near skarn contacts they are otherwise essentially unaltered. Porphyry molybdenum deposits as defined by Clarke (1972) have not been reported in the Caribbean area.

Jan 1, 1978

By Russell W. Mumford

LITHIA compounds have a place in pharmaceutical and other chemical industries and lithium minerals in glassmaking and ceramics. The metal, although rare, is used to a minor extent in alloys. During the nearly 50 years of production of lithium minerals in the United States, the silicate mineral spodumene has continued as the chief source of raw material for the manufacture of lithium salts. Although twice as much lepidolite, a lithium mica, has been mined, most of it has been used in the making of certain types of glass. Amblygonite has been an additional but minor source of lithium compounds. Triphylite, petalite, and zinnwaldite have also been utilized in the past. All of these commercial lithium minerals contain low percentages of lithium (Table 1). In 1938, a new raw material for manufacture of lithium compounds made its appearance. This product was crude dilithium sodium phosphate (Li2NaPO4), obtained as a by-product of manufacture of potash and soda chemicals from the brine of Searles Lake, California. Searles Lake, which is now dry, lies in the extreme northwest corner of San Bernardino County, California, and consists of a large mass of salts. It was estimated by the United States Geological Survey that the crystal body contained about 25 pct voids, which are filled with a saturated brine. The brine consists mainly of the sulphates, chlorides, carbonates, and borates of sodium and potassium. Several other acid radicals, including phosphates, are present. Lithium is present in the brine in an amount corresponding to 0.01 15 pct Li2O. In the course of evaporation of water from the brine, during the process of manufacture of sodium and potassium chemicals, dilithium sodium phosphate crystallizes out and is recovered by a flotation operation. The lithium concentrate is filtered and dried and is then ready for shipment. It analyzes from 19 to 21 pct Li2O and now constitutes the highest known grade of crude lithium material. It is and will continue to be a major source of lithium for manufacture of lithium products. The variation in lithia content of the commercial minerals as mined is due to replacement of the lithia by soda and potash, to partial alter-

Jan 1, 1949

By B. A. Wilcox, A. H. Clauer

The tensile and creep deformation characteristics of fiber reinforced composites have been studied, primarily at room temperature. The matrix was an alloy of Mg-14 wt pct Li-1 wt pct Al (LA141A alloy) and the reinforcing fiber consisted of continuous wires of a high strength precipitation hardening stainless steel (AFC-77 alloy). The ultimate tensile strength and strength-to-density ratio of composites were much improved over that of the mmix, both at room ternperatwe and up to 200°C. Creep studies at room temperature revealed logarithmic weep behavior for wires and composites and steady state creep for the nonreinforced matrix. It was concluded that creep of the fibers controlled composite creep. The instantaneous logarithmic weep rate of the composite, 6, was related to the average tensile stress on the fibers, where n = 3.4. Mg-Li alloys are the lightest structural metals commercially available, e.g., the alloy LA141A (Mg-14 wt pct Li-1 wt pct Al) is 27 pct less dense than beryllium Although Mg-Li alloys have moderate tensile strengths at normal strain rates and ambient temperature, their creep strength is relatively poor, even at room temperature. Reinforcement by fibers offers a means of increasing the tensile strength as well as overcoming the limitations of low creep strength. With a proper choice of reinforcing filament, composites could be designed with higher strength-to-density and modulus-to-density ratios than the matrix alloy. This communication reports a study on the tensile and creep characteristics of alloy LA141A reinforced with continuous wires of a high-strength precipitation hardening stainless steel (AFC-77 alloy). The matrix has a bcc structure, with possible precipitates of AlLi and MgLi2A1,3 and is ductile at room temperature Stainless steel wire was chosen as the -reinforcing filament since previous work at Battelle4 showed that a good bond between wire and matrix could be produced in this system. For all volume fractions of reinforcing wire, the theoretical composite strength-to-density ratio is greater than that of the matrix and the modulus-to-density ratio is somewhat lower than that of the matrix. EXPERIMENTAL PROCEDURES The 0.004-in. diam AFC-77 wire was obtained from two suppliers: National-Standard Co.* and Crucible 0.13 Si, 0.18 V, 0.011 P, 0.012 S, balance Fe. In the as-received condition, wires from both sources had room-temperature ultimate tensile strengths of 585,000 to 590,000 psi with approximately 2 pct total elongation and 40 pct reduction in area. Composite preparation was accomplished by the vacuum infiltration technique. This involved placing the continuous wires in a mild steel tube (1/8-in. ID), capping one end of the tube with a sheet of the matrix alloy, and evacuating the other end of the tube. When the capped end was placed in a crucible of the molten matrix alloy and held for 31/2 min at 70O°C, the liquid metal was drawn up the tube approximately 7 to 8 in. A cross-sectional view of a typical composite is shown in Fig. 1. This preparation technique promoted excellent bonding between the matrix and wires, and porosity was rarely observed. Test specimens for both creep and tension studies were prepared by machining off the steel tube. Tensile tests on the wires and composite specimens were made in an Instron using a cross-head speed of 0.01 in. per min. The composite specimens had no reduced section and were held in self-tightening grooved serrated grips. Most of the specimens broke in the effective 1-in. gage section. Even though several tests fractured in the grip section, their ultimate strengths were essentially the same as those of specimens which fractured in the gage section. Creep specimens of the composite were gripped in a similar manner, and

Jan 1, 1970

By C. S. Matthews, P. Hazebroek, H. Rainbow

It ha been suggested that lormation fractures created by well stimulation treatments will adversely affect sweep-out efficrency in injection operations. Fluid-flow model studies involving vertical fractures of various lengths and fluid systems of various mobility ratios have been carried out to study this subject. In addition, limited data have been obtained on one model containing a horizontal fracture. It was found that relatively long and highly conductive fractures (not generally obtained fracturing operations) were required to affect the sweep-out efficiency substantially. In a given case in the field an approximate distinction can be made between the presence of long conductive fractures and shorter or less conductive ones. This is done with pressure build-up analyses along with data on the relationship of fracture length and conductivity to well productivity. This type analysis shows that usually the fractures induced are either short or of limited conductivity and therefore do not damage sweep-out efficiency. INTRODUCTION Improved well productivity and in-jectivity can frequently be exploited in injection operations. Higher total throughput can yield improved economics. On occasion, the achievement of an increased productivity or injectivity in specific wells can bring about a more uniform sweep of the reservoir. Higher rates can be exploited particularly in water floods of "depleted" reservoirs where a rapid "fill-up" is desired and where low pressures contribute to low well productivity. The creation of fractures local to the wellbore is an excellent means for achieving these objectives. Even though fracturing has been employed in some floods with success,1"3 there still seems to be some reluctance to employ this tool for fear of undue damage to the flood pattern and ultimate recovery. We therefore need to examine the influence which fractures of varying length may have on flood performance and then determine the length of fractures which obtain in the field with conventional fracture treatments. A substantial influence of fractures on the recovery obtained at breakthrough of the injected fluid has been presented by Crawford and Collins for equal fluid mobilities for the line-drive pattern.4,5 In addition, the influence which a fracture has on the production performance after breakthrough and on the ultimate recovery warrants consideration in reaching a conclusion concerning the use of induced fractures in flooding operations. This report presents this type of data for the five-spot injection pattern for several fluid mobilities. In arriving at some conclusion concerning the fracture lengths obtained in field operations we must examine the performance characteristic most affected by the fracture. This is the change in the flow system as reflected in the change in productivity and pressure build-up behavior. A study of these changes is also presented in this report. RESERVOIR ANALOGS The X-ray shadowgraph technique, employing miscible displacement in porous models, has been used in the study of the influence of fractures on pattern sweep-out efficiency. The X-ray shadowgraph procedure is described in detail in an earlier report8. Fractures were represented by leaving the proper portion of the model surface exposed to either injection or production. This assumes the fracture resistance to be negligible compared to that of the formation. Actually the flow resistance in propped fractures obtained in the field is sometimes not negligible so that the results with this model indicate the maximum influence of the fracture. Two types of models were necessary to represent vertical fractures in a five-spot flood. These pattern elements are illustrated in Fig. 1. In studying the influence of the horizontal fracture, only one well spacing length to thickness ratio of 50 was used. The pool unit of a Carter Electric Analyzer was used in studying the influence of fractures on productivity and build-up behavior. The square drainage system of a well was represented by a network of 576 elements of equal volume and resistance. One-fourth of this drainage area was studied as a model unit using a network of 144 condensers and resistors. Vertical fractures were represented by a shunt directed from the well perpendicular to the drainage boundary. Horizontal fractures were represented by a circular shunt. Resistance of a shunt was varied in representing different conductivities for the fractures. FRACTURE DIRECTION AND LENGTH The direction at which a vertical fracture extends into the formation and its length and conductivity influence the sweep behavior. The two

By S. C. Jones, J. A. Davis

This paper describes displacement mechanisms of micel-lur solution slugs, displuced by a thickened water "mobility buffer", in a glass micromodel and in consolidated Berea sandstone cores. Colored motion pictures, taken through a microscope, recorded interactions on a pore-to-pore bash in the micromodel. Production and differential pressure data from consolidated cores previously waterflooded to residua1 oil saturation revealed displacement mechani.sm.s macroscopically. Oil is displaced miscibly, while interstitia1 water is displaced immiscibly by the injected micellar. solution slug. Part of this water is dispersed and carried near the lead ing edge of the .slug, and some may remain as a residual saturation. Thickened water displaces any residual water. It also emulsifies with the. slug material, thereby displacing it. The displacement sequence forms banks of oil and water with relatively constant fractional flows, saturations, and mobilities. The mobility of oil and water flowing ahead of the .slug defines .slug viscosity required for stable displacement. Equations are presented that describe. several aspecis of the displacement flow behavior: oil breakthrough, oil cut during production of the stabilized bank, breakthrough of banked water and the resulting decreased fractional flow of oil, fluid mobilities, etc. Breakthroughs, calculated from the equations, are compared with experimental data. Slugs of micellar sollution, ranging from 1 to 5 percent PV, produced unusually high oil recoveries (up to 100 percent) in previously waterflooded consolidated cores. Investigation of the effect of mobility buffer size on oil recovery indicated that recovery is reduced in 3-in. X 4-ft cores for mobility buffer sizes .smaller than 50 percent of the pore volume. Introduction A new oil recovery process,* conceived in 1962, utilizes a slug of micellar solution' that has sufficient viscosity to avoid an unfavorable mobility ratio with respect to the oil and water it displaces. These micellar solutions are composed of hydrocarbons, water, and surfactants, and may contain electrolytes and co-surfactants. The micellar solution is displaced by a "mobility buffer". The mobility buffer is a bank of reduced-mobility fluid, preferably an aqueous polymer solution. The entire system is displaced by unthickened water. This paper describes some of the microscopic and macroscopic displacement mechanisms observed during laboratory development of the fluids for a potential field test. Microscopic phenomena were observed photographically in a specially constructed glass flow model and macroscopic data were taken from constant rate, tertiary displacements conducted in Berea sandstone cores. Qualitative Description of Micellar Solution Flooding This section qualitatively describes displacement mechanisms that occur when a slug of micellar solution is injected into a previously waterflooded core. The slug completely removes oil from the portion of core it contacts, and banks oil in the process. The oil saturation in this bank and the flowing WOR reach definite, fixed values that are determined by water and oil mobilities and slug characteristics. This zone of constant WOR and oil saturation will be called "stabilized oil bank" in the following discussion. When this stabilized bank reaches the outlet end of the core, the oil cut jumps from zero to a constant value equal to the fractional flow of oil. Saline water has little or no solubility in the slug. Because of this. the slug displaces in-place brine immiscibly. During slug injection, most of the brine is displaced ahead of the slug, some is carried along in the leading portion of the slug, and part of the brine may become immobile. The immobile, residual brine is later miscibly displaced by thickened water. Displacement of all the oil and only part of the water during slug injection results in a higher fractional flow of oil ahead of the slug than occurs when all the water is displaced after injection of thickened water is begun. The slug spontaneously emulsifies fresh (low-salt content) water. By emulsification, the slug can become infinitely diluted, and hence totally displaced, by thickened water. Fluid saturations in the core are shown schematically in Fig. 1. Parts A and B show conditions before and after the start of the thickened-water injection, respectively. Since thickened water displaces any residual brine by-

Jan 1, 1969

By M. V. Lowry

This paper outlines the economic considerations that led to the recent installation of a thickener at St. Joseph LeadCo.'s Balmat, N.Y. mill. To incorporate storage of concentrates, they decided upon a single, unusually deep tank to be used for both storage and thickening. The abnormally high rake lift required was achieved by the novel feature of having the entire drive platform raise and lower. Initial operating problems are described along with the satisfactory solutions. Total costs for concentrate handling before and after installation of the storage thickeners are compared. In Northern New York State, the St. Joseph Lead Co. conducts a 2100 tpd zinc mining and milling operation at its Balmat Plant. Conventional crushing, grinding, and flotation is used to produce a zinc concentrate. For 32 years, from 1930 through 1962, the plant operated with the concentrates going directly from flotation to the filtering, drying, and loading facilities. All of the concentrate handling equipment, therefore, had to operate 24 hrs per day. It also had to accommodate wide fluctuations in tonnage, due to variations in the grade of ore. Many problems were thereby encountered in filtering and drying, but it was never concluded that the cost could be justified for installing a conventional, large diameter thickener. Finally, in 1963, they installed an unconventional thickener that is unusual in several respects. The tank depth is 16 ft instead of the normal 8 ft. The rakes are raised and lowered by having the main drive gear located on a movable platform. Automatic controls are programmed to raise the drive platform and rakes during one shift of storage. During the next two shifts of withdrawal, the controls are programmed to lower the drive platform and rakes. After three years of operating this unique storage-thickener, the conclusion is that a correct choice was made from several alternative schemes for storing concentrates. The various considerations involved in the final selection will here be analyzed, and the design features and installation details will be de- scribed. Operating problems and modifications made to the equipment will next be considered, and finally the effects upon filtering, drying, and loading will be reported. SELECTION CONSIDERATIONS Even without a thickener, concentrate handling had become reasonably efficient at the Balmat Mill by the year 1962. A tonnage that varied between 6 and 25 tph was being handled fairly satisfactorily. The filter cake moisture of 8%% seemed quite respectable, except that two large filters were usually in service. Three filters often had to be operated in order to prevent excessive filter overflow with consequent loss of values. This situation occurred when zinc concentrates from flotation exceeded 20 tph and when filter cloth blinding developed. Over the years, numerous small improvements had been effected, such as: selection of a filter cloth with better flow characteristics; addition of flocculant to the filter feed; and, in 1953, the smallest of three drum filters was replaced by a five disc, 8' 10" diam filter with a bottom agitator and snap blow. As another example of fairly efficient operation, the oil-fired dryer was doing a seemingly satisfactory job of further reducing the moisture content to an average of 3%. However, there were often considerable dust losses when the tonnage suddenly dropped off to 6 tph. At high tonnage rates, the resulting high moistures of 4% and 5% caused difficulties due to concentrates sticking and freezing in chutes leading to the box car loaders. (Drying of concentrates is justified because of the high freight rate for the long shipping distance to the company owned smelter at Josephtown, Pa. near Pittsburgh.) It was long realized that installation of a thickener would permit the subsequent steps of concentrate handling to proceed more smoothly and would alleviate the problems existing in the filtering, drying, and loading operations. It was also realized that even a slightly lower filter cake moisture could mean considerable savings in fuel oil. However, all these factors were never quite sufficient to warrant the expense of a thickener until three more considerations were added to the picture. First, the advent of flocculants meant that a thickener of relatively small area could now be considered. Secondly, a complete renovation of the zinc flotation circuit was made between 1957 and 1961. The

Jan 1, 1967

By K. F. Veith, R. L. Marovelli, T. S. Chen

An analytical study is made of thermal stress distribution in a thin circular disc subjected to a peripheral thermal shock at various rates of heat transfer. The problem is of importance in predicting the thermal shock response of a rock body of finite size. The theoretical analysis is based on radial heat flow by conduction in the disc and heat exchange by convection between the disc and the surroundings. The case of constant properties and plane stress is treated. Solutions of the stress distribution are presented for both cooling and heating shocks and an average stress theory is formulated. Preliminary experimental verification was obtained from the results of shock tests on thin rock discs insulated on both flat end faces so that heat exchange took place through the exposed peripheral surface. Physical properties vital to the analysis are Young's modulus, tensile strength, coefficient of linear thermal expansion, thermal diffusivity and thermal conductivity. Plots of these properties are presented. Historically, thermal energy has been used for primary rock removal throughout the ages. Although it is not widely known, the fire-setting method of thermal rock fragmentation was still in use 100 years ago in systematic underground mining operations in Scandinavia.' There, the availability of cheap labor and abundant wood fuel made the method competitive with the early blasting powders. By 1880, as high explosives replaced powder, use of the method declined and it was finally abandoned about 1885. Only 40 years ago, some experimental fire-setting methods were used for rock removal underground at Pribram and Zinnwald in Central Europe.2 Compressed air-oil burners replaced the earlier wood fuels. About 15 years ago, gaseous oxygen-oil burners were introduced in the United States and gained acceptance for difficult blasthole drilling and some quarry opera- tions. At present, there is renewed interest in the compressed air-oil burner designs. The literature included information on thermal secondary processes for rock weakening or particle liberation3,4,5,6,7,8 on thermal spallation of rock 9,10,11,12,13 and on the thermal fracture of materials other than rock. The 1955 Symposium on Thermal Fracture14 and the later work of Hassel-man, cover recent developments in thermal shock investigations on brittle ceramics. Although the number of published analytical and experimental investigations conducted on ceramic and refractory materials is large, the literature reveals that there is a lack of information on both the theoretical and actual response of rock to thermal shock. Many of the thermal shock studies on ceramic and refractory bodies are based on the case of heat transfer at the solid's surface by convection in either liquid or air. A similar heat transfer situation was adopted for a theoretical analysis of the thermal stresses in a thin circular disc subjected to a peripheral thermal shock. Experimental thermal shock tests were then conducted on rock specimens to check the analytical results. Specially insulated quartzite, basalt and taconite discs were shocked in either liquid or still air bath at various rates of heat transfer. The work was done in order to resolve the question as to whether theoretically determined tensile stresses are actually realized in a finite rock body undergoing thermal shock. Specifically, if theory predicts that the tensile strength of a rock should be exceeded in a particular type of controlled thermal shock, will fracture occur? This information is needed by Bureau researchers working on thermal and electrical rock fragmentation methods. The object of this paper is to present the main features of the theory and procedure being used in the authors' approach to quantitative prediction of rock response to a thermal shock. THEORETICAL ANALYSIS In the analysis to follow, simple geometry of a thin circular disc is considered. The disc is assumed to be isotropic, homogeneous and perfectly elastic, and to have constant thermal and mechanical properties. The effect of radiation is neglected so that heat is transferred by conduction inside the disc and by convection with its surrounding. In addition, the end

Jan 1, 1967

By Ralph Hultgren, Prodyot Roy

Manganese vapor pressures from 1250° to 1500°K were measured by conventional Knudsen and torsion-effusion methods in twelve Fe-Mn alloys with compositions from 9 to 80 at. pct Mn. The Knudsen re-sults agveed approximately with previous measurements found in the literature which indicated the solutions were nearly ideal. However, except for the higher manganese compositions, the initial torsion readings indicated much (up to 50 pct) higher vapor presszcres than the Knudsen method. These high readings decreased steadily with time. The results are interpreted as due to depletion of surface concentration of manganese during evaporation. Thus the initial torsion readings are the most nearly correct and Knudsen methods on alloys are to be regarded with suspicion unless it can be demonstrated that diffusion rates are rapid enough to replenish surface concentrations depleted by evaporation. For the lowest manganese contents and highest temperatures, depletion causes initial torsion readings to be too low. FEW thermodynamic data are available for alloys of the high-melting transition metals due primarily to experimental difficulties at the high temperatures involved. Measurement of vapor pressure is one of the most promising techniques to be applied to this problem. From the vapor pressure of a component of an alloy phase, its activity or its partial molar Gibbs energy can be directly calculated. From measurements over a sufficient range of temperatures and compositions the partial and integral Gibbs energies, enthalpies, and entropies may be determined through Gibbs-Duhem integration. For solid phases of variable composition, which commonly are found in alloys, measured vapor pressures are low because of depletion of the surface concentration of the more volatile component as it is selectively vaporized. Diffusion from the interior tends to restore the depleted concentration. The seriousness of the effect depends on the relative rates of diffusion and vaporization. Although depletion has been recognized as a factor,' direct measurements of its rate are lacking and quantitative estimates of its effect on measurements are uncertain. In the present work the vapor pressures above a series of Fe-Mn alloys have been measured by the torsion-effusion method. This method permits a measurement of the vapor pressure of manganese as soon as the sample comes to temperature and continuously throughout the run. The rate of decline of the apparent vapor pressure measures the rate of depletion and the torsion reading at zero time should be correct. At high manganese concentrations (70 and 80 at. pct Mn), the torsion reading remained nearly constant; surface depletion was negligible. There was a slow drop in measured pressure due to bulk loss of manganese from the sample. However, for lower manganese contents, especially at high temperatures, the depletion effect was considerable and the apparent vapor pressure decreased steadily with time. For these alloys the Knudsen method should give pressures which are too low. The measurement of pressure in the Knudsen method cannot be made until enough manganese has been vaporized to be weighable. The Knudsen result is therefore an integrated average between the initial and final vapor pressures. To verify this, conventional Knudsen measurements were also made with results in approximate agreement with previously published Knudsen measurements for these alloys. As expected, for the lower manganese contents the initial torsion readings of pressure were as much as 50 pct higher than the Knudsen. THE APPARATUS The apparatus, shown in Fig. 1, is capable of operating to temperatures up to 2000°K. A vacuum of 5 x 10"6 mm Hg can be maintained. Temperatures were measured to +3° by a W-Re thermocouple placed in the dummy cell, N. The torsion cell consisted of two alumina crucibles with holes in their covers. They were placed in the molybdenum holder shown suspended from the torsion wire. Rectangular torsion wires (1 by 4 mm) were found to have superior sensitivity and less residual distortion than circular (2-mm-diameter) wires. The precision of angular measurement was found to be *0.025 deg; the variation is no doubt due to temperature fluctuation and vibration. For the Knudsen experiments the alumina cell was set on the support, N. SAMPLE PREPARATION 800-g samples were prepared by melting together electrolytic iron and electrolytic manganese and pouring the melt into a water-cooled copper mold. Melting and pouring were done under a helium at-

Jan 1, 1965

By Frank Doxey

AT Dominion Steel & Coal Corp. it has long been recognized that continued mechanization of mine operations is necessary in the Pictou, Cumberland, and Sidney coal fields of Nova Scotia. The varied physical conditions in these fields call for special consideration of individual cases before planning is finalized. Because standard equipment cannot be procured which would operate successfully, many experiments have been necessary over the years to keep pace with the progress made in other countries. There are two mines, producing 2000 tpd, located in the Pictou coal field. The field is badly distorted and crossed by many faults. Seams are highly inclined and irregular and vary in thickness from 5 to 40 ft. Entries are difficult to maintain because of squeezing of the coal. ribs and movement of the roof and pavement. Output from the three operating mines in the Cumberland field is 3000 tpd. The field is highly inclined, inclination varying from 12° to 32°. Overlying beds consist of shales and massive sandstone lenses of extreme toughness and are responsible for bumps when the stresses are relieved by extraction. At greatest depth these are among the deepest coal workings in the world. Depth of cover ranges from 2300 to 4000 ft. This prohibits room-and-pillar working and necessitates longwall operation. Working of contiguous seams concurrently to maintain output increases the already difficult conditions. The Sydney field, with a frontage of about 30 miles, is the most important of the Nova Scotia coal fields. With the exception of one small area it is now wholly submarine. Output is approximately 21,000 tpd. Seams are 21/2 to 8 ft thick, and cover in the areas varies from 600 to 2300 ft, with an average of 1500 ft from sea bottom to the top of the seam. The seams dip in a seaward direction, pitches ranging from 6" to 4.0". The shoreline is the last place of entry to the seams and distance from the bank to the working faces is generally over 3½ miles, in some cases as much as 6½ miles. Ventilation is a problem and requires the construction of large permanent airways. Getting and Loading Coal: In 1925, in view of heavy pressures exerted by thickness of cover overlying the seams, roadways and pillars of the room-and-pillar system being worked began to break up and coal was lost. It was decided that a change in the method of extraction in areas with heavy cover was necessary, and experiments were made with many short walls and longwalls varying between 90 and 250 ft. Trial and error proved that the best operating length was between 400 and 500 ft, delivering all coal to the dip, with roadways to the face following a level course. The change-over was gradual, and the technique of roof control developed with the system, so that falls to the face are now very infrequent. An advantage of longwall mining is that it yields 95 pct extraction, especially important in coal seams of high quality or in seams where faults or disturbances restrict the workable areas. This percentage of extraction is based on the fact that the longwall advancing system takes development faces where pitch permits instead of driving headings and leaving roadway pillars. This system yields high tonnage during development and limits loss in extraction to duff left during operations. Accompanying disadvantages, on the other hand, are the heavy construction cost of main roadways and the necessity of driving all new flank face roadways through the gob. If the main roadways are driven through the solid, and large enough pillars are left on each side for protection against flank face weights, then the width of solid coal is approximately 1700 ft. This represents 10.6 pct of the coal available, or 89.4 pct extraction of the whole. These pillars, however, are of such size that they provide a useful pillar drawing area as a final operation of the mine. It may be that although the seam cannot be generally mined by the room-and-pillar method, it can be adapted to

Jan 1, 1955

By S. L. Lopata, E. B. Kula

A variation of yield and tensile strength with direction has been noted in heat-treated 4340 steel which had been warn-worked by rolling in the austenitic condition prior to quenching. Measurements by X-rays showed a preferred orientation of martensite crystals. Various ideal preferred orientations of martensite were calculated by assuming a preferred orientation for austenite and transforming this to martensite by the Kurdjumov -Sachs and Nishiyama relationships. Comparison with the measured preferred orientation showed that the ideal rolling texture for austenite in 4340 steel could be expressed as a (112) [111] texture with a component of (110) [112]. No evidence was found for any fiber axis in the rolling direction, or fop- a (123) [412] texture. The observed martensite pole figures can be adequately accounted for by these ideal austenite textures and by the Kurdjumou-Sachs or Nishiyama transformation relationships between austenite and martensite. ALTHOUGH preferred orientations are found in cold-rolled steel sheet and in many nonferrous metals, they are not generally encountered in wrought, heat-treated high-strength steels, since such steels are generally not cold worked sufficiently to develop a strong texture, and any texture that is present is removed during heat treatment by the phase transformations taking place. This report gives details on a preferred orientation found in warm-rolled and hardened 4340 steel. In a recent study, a special combination heat-treating and working technique was used in which 4340 steel was deformed in the austenitic condition, and before re crystallization of the austenite could occur, quenched to form martensite.' Since the austenite was unrecrystallized, it was cold worked and hence could have contained a preferred orientation which could be transmitted to the martensite on quenching, and this in turn could be manifested as a directionality of mechanical properties. Such a directionality of properties was found as a result of working, and this prompted an X-ray study of the preferred orientation. Literature Survey— Rolling Texture in Face-Cen-tered-Cubic Austenite—M a preferred orientation is found in a rolled and hardened steel, it is first appropriate to consider what texture existed in the austenite as a result of the rolling but prior to the transformation to martensite. The changes taking place as a result of the austenite-martensite transformation are then considered. In view of the instability of austenite in 4340 steel at low temperatures, no direct determination of the austenite texture was made. However, an estimate of the texture for austenite in 4340 steel may be made by considering the textures found for other face-centered-cubic metals. Barrett' has reviewed the rolling textures for many materials. The most common orientation in face-centered-cubic metals has the (110) planes parallel to the rolling plane and the [112] directions parallel to the rolling direction, or (110) [112]. Other orientations found are (112) [111], as well as (100) [001], (110) [001], and others. Beck and his co-workers, using quantitative pole figures, report that (123) [121],3 later corrected to (123) [412],4 better describes the ideal orientation. smallman5 reported that the ideal preferred orientation for high-purity face-centered-cubic metals is (123) [121], but that there is a transition to (110) [112] as solid solution elements are added. The latter texture tends to occur more readily at lower temperatures. This transition between the two textures was explained by differences in the slip characteristics with concentration or temperature. More recently, Jones and Fell6 concluded that the (123) [412] texture for face-centered-cubic metals could equally well be represented by a mixture of (110) [112] and (112) [111] textures, and hence it had no physical reality. From the above results it can be seen that there is no agreement on the "ideal" texture for fcc metals and, hence, no firm basis for assuming a texture for austenite in 4340 steel. Therefore, the orientations (110) [112], (123) [412], and (112) [111] have been considered in the following.* *The (123) [4121 is identical to the (123) [121] rotated 90 deg. Orientation Relationship between Austenite and Martensite—When martensite forms from austenite, certain crystallographic planes of the martensite are parallel to planes in the austenite. This orientation relationship was first determined by Kurdjumov and

Jan 1, 1960

By F. Weinberg, E. H. McLaren

Dilute binary alloys have been solidified under controlled thermal conditions, and solute distributions, temperatures during freezing and melting, and the position and morphology of the solid-liquid interfaces have been examined. Binary Zn, Sn, and Pb based alloys were investigated with solute additions of AgU°, AU°, Sb'24, TlZo4, snH3, and Zns5. Approximately 150 cc of metal was used in each ingot. Appreciable solute segregation occurred in most of the ingots, depending on the solute concentrations, distribution coefficients. and freezing conditions of the alloys. Measurements were made of the general solute distribution by sectioning layers of material from the ingot circumference and counting the activity of each layer. Local segregation was detected by autoradiographic techniques. Freezing and melting curves for the same alloys were obtained by precision resistance thermometry. These curves are related to the corresponding measured solute distribution curves and those calculated from theoretical expressions. The position and morphology of solid-liquid interfaces during freezing were determined by both decanting and quenching techniques. The results indicate the manner in which freezing and remelting occurred under the conditions investigated. If an isomorphous dilute binary alloy is solidified or melted under equilibrium conditions, the concentration of solute in both solid and liquid would be uniform at all stages in the freezing process. The solute concentrations during freezing could be determined from the phase diagram of the alloy, and the freezing curves would have an alloy slope defined by the solidus and liquidus points. In practice, however, solidification under equilibrium conditions rarely, if ever, occurs, primarily because of low rates of diffusion in the solid and incomplete mixing in the liquid. As a result, the solute distribution and the shape of the freezing and melting curves obtained in a given system depends on a number of factors. These include, in addition to the extent of diffusion and mixing, the initial solute distribution and concentration, the distribution coefficient, the rate of freezing or melting, supercooling of the liquid, the morphology of the solid-liquid interface, and the effect of annealing. The purpose of the present investigation was to determine, experimentally, actual solute distributions and thermal curves for a series of dilute binary alloys, using tracer techniques to determine the solute distributions and precision resistance thermometry for the temperature measurements. In addition, observations were made of the positions and morphologies of the solid-liquid interfaces during freezing and remelting. The distribution of solute in a dilute alloy, assuming complete mixing in the liquid, and negligible diffusion in the solid, is given by1 where Co is the mean solute concentration of the alloy, C, is the solute concentration in the solidg is the fraction of the ingot solidified, and ko is the equilibrium solute distribution coefficient (assumed to be independent of concentration for dilute alloys). For the case of partial mixing, ko can be replaced by an effective distribution coefficient k. If solute transport in the liquid is assumed to be entirely due to diffusion, with negligible diffusion in the solid, then the solute distribution in the solid is given by Tiller et a1.' as where R is the rate of advance of the solid-liquid interface, D is the solute diffusion coefficient in the liquid, and x is the position of the interface from the start of freezing. The temperature at the interface TI is related to the solute concentration of the solid at the interface C, by the expression where Tm is the freezing temperature of the pure solvent and ml is the slope of the liquidus for the binary alloy being considered. Accordingly, by relating TL to the actual temperatures measured in the present experiments, solute distributions can be deduced from the temperature measurements. Using the above expressions, the measured solute distribution of a given alloy may be compared to the theoretical distributions, as well as to the distribution calculated from the observed freezing curve. EXPERIMENTAL The solvent materials used in making up the binary alloys were C. P. New Jersey zinc (99.999 pct), Vulcan Extra Pure Tin (99.999 pet), and Tadanac lead (99.998 pct). The solute elements were of 99.99 pct purity or better, and were activated in the

Jan 1, 1963

By J. D. Alexander, W. L. Martin, J. N. Dew

This paper presents data obtained using a flood-pot technique to determine the fuel available and the corresponding theoretical air requirements for in situ combustion of crude oils. Since the technique is relatively quick and easy, it is a practical and convenient tool for evaluating reservoirs as fireflood prospects. It is also a research tool which facilitates systematic study of the variables affecting fuel availability and corresponding air requirements. The understanding of these variables is of prime importance to those concerned with the technical and economic development of in situ combustion as an oil-recovery process. The experimental results show conclusively that the fuel available for in situ combustion is not a constant but, rather, varies with crude-oil characteristics, porous-medium type, oil saturation, air flux and time-temperature relationships. Thus, the fuel availability for specified field applications should be determined using actual reservoir crude and core material and the process conditions expected during in situ combustion in the reservoir. INTRODUCTION In situ combustion is a thermal process for recovering crude oil from reservoirs. The thermal energy released during the combustion of a small amount of the oil in place aids in the displacement of the remaining oil. Numerous articles have been published describing the in situ combustion process giving detailed results of laboratory and field experiments.10 In order to engineer an in situ combustion project, a number of important factors must be considered and determined. These factors include: (1) the amount of fuel consumed per unit of reservoir volume swept by the combustion zone, (2) the composition of the fuel consumed, (3) the amount of air required to consume this fuel, (4) the portion of the reservoir swept by the combustion zone, (5) the appropriate air-injection rates and pressures, (6) the amount of oil that will be recovered, (7) the rate of oil production and (8) the operating costs. Nelson and McNiell1 recently have described a procedure which utilizes laboratory combustion-tube data as a basis for the calculation of some of these design factors. Various authors have attempted to describe the in situ combustion process mathematically, and considerable progress has been made. Analytical solutions to the problem of heat transfer from a moving combustion front have been obtained for linear and radial systems."-' All of the published results involve the assumptions that: (1) fuel concentration is constant throughout the reservoir, or that fuel concentration is inversely proportional to the velocity of the front for a given rate of oxygen consumption; and (2) the fuel reacts instantaneously with injected oxygen, while liberating a constant amount of heat per unit weight of fuel at all temperatures. It seems both desirable and reasonable to test the validity of these assumptions experimentally. This paper presents laboratory data which were obtained by means of a "fire flood-pot" method for determining fuel availability and composition, and the corresponding theoretical air requirements for in situ combustion of crude oils under variable conditions. The mechanics of the method are similar to a conventional tube-run experiment.' The important differences involve the size of the reservoir model used and the method for providing the experimental environment. The new method subjects conventionally-sized core samples or unconsolidated sands to a programmed environmental sequence similar to that experienced by a similar volume of rock during the approach and passage of a combustion front in a long tube or in an oil reservoir undergoing in situ combustion. Restored-state samples can also be used. The small samples and relatively simple techniques involved allow an experiment to be set up, run and calculated in about three 8-hour days. This is a considerable improvement over long-combustion-tube techniques which can require several days to run and several more work days to set up and calculate. All the runs presented were run at 40-psig injection pressure. Pressure was not considered as a variable for these experiments, since we previously had found that it had only a small effect on fuel availability up to 600 psig.APPARATUS AND MATERIALS APPARATUS The fire flood-pot apparatus consists of a consolidated

By D. W. Fuerstenau, P. C. Kapur

The kinetics of green pelletization in a laboratory balling drum have been studied, using pulverized limestone as a model system. The growth characteristics of green pellets were found to be extremely sensitive to the moisture content of the material. Empirical kinetic equations, which incorporate a function of specific surface of the pellets as the criterion for growth potential, have been found to describe growth in a nucleation region and in a ball growth region. The rate constants in the kinetic equations are strongly dependent on the moisture content of the material being pelletized. Size distributions of the balls at different stages of pelletiz-ing are also discussed. In many industrial chemical processes, particulate matter can only be utilized if it is in an agglomerated form, such as pellets. Pelletizing is now widely used in iron ore technology1, and it has also been applied to a number of diverse fields such as the production of cement-kiln feed2, fertilizers3, and fluorspar4. Recently, it has been proposed to pelletize dispersion-type ceramic nuclear fuel elements5. In iron ore technology, for example, the production of agglomerates by pelletizing involves two major steps: 1) the preparation of green balls by rolling particles in a suitable balling device and 2) the firing of the green balls to form compact, strong bodies upon sintering. The critical step in a successful iron ore pelletizing operation is generally considered to be the balling operation1. In this paper, which is not concerned with the sintering of green pellets, the words green pelletizing and balling will be used interchangeably. Green pelletizing, or balling, will be defined as the process of forming larger bodies by rolling fine particles on a surface without the application of direct pressure. Two recent literature surveys6" indicate that in spite of the considerable amount of industrial pelletizing, very little is known about the fundamental principles of balling and its kinetics. The first reported research on the kinetics of pelletizing is the work of Newitt and Conway-Jones8. Using silica sands of different sizes in a batch laboratory balling drum, they found that the average green pellet diameter increased linearly with time at constant drum speed, and qualitatively the growth rate increased with moisture content. Generalized conclusions cannot be drawn from their research since the materials which they pelletized were sand and sand-silt mixtures rather than comminuted materials. Moreover, Newitt and Conway-Jones used testing sieves to estimate the size distribution of the green pellets, and this technique limited the range over which they could study the growth kinetics of the pellets. Bhrany and co-workers9 investigated the kinetics of balling iron ore fines on disk pelletizers ranging in diam from 1 to 18 ft. In their investigation, balling was carried out as a continuous operation, and growth kinetics were studied in terms of retention time of the material on the disk. Although the feed material in their study was quite coarse (the maximum size being about 1/2 in.), they also found qualitative relationships between pellet growth and water content, and feed size. In the present investigation, a number of innovations were introduced that refined the experimental measurements and established the reproducibility of balling experimentation. This enabled extension of the range of measurements to include study of agglomerate nucleation phenomena in the fractional mm size. This paper presents a detailed analysis of the nucleation and growth of green pellets in a laboratory balling drum. MATERIALS AND METHOD Pulverized limestone of specific gravity 2.72 was used as a model system in these studies. It has already been established that the balling characteristics of limestone and silica are similar to those of iron ore concentrates 2,8,10, depending on physical, rather than chemical, properties of the particles. The size distribution of the limestone was determined by a wet-dry sieving technique in the sieve range and by a sedimentation balance in the sub-sieve range. Fig. 1 presents the size distribution of the limestone used in this research. This figure shows that the material is finer than 200p (65 mesh) and that 25% of it is finer than 12. The specific surface area of this powder, as measured by BET gas adsorption methods,

Jan 1, 1964

By F. D. Rosi

The plastic properties of extended silver and copper crystals of varying purity were studied as a function of crystal orientation in the early stages of flow. Variations in the gross shape of the shear stress-shear diagram and in the properties of critical Variationsshear stress and shear-hardening coefficient were correlated with changes in slip-band developments. The phenomenon of work hardening is discussed in terms of the existing dislocation theory. IT appears certain from the early studies on the deformation characteristics in metal crystals1-3 that plastic flow takes place in a preferred crystallo-graphic slip system which is determined by the geometry of the crystal (law of maximum shear stress), and that the value of shear stress for this system is independent of crystal orientation (law of critical shear stress). Experimentally, it has been demonstrated further that the law of critical shear stress can be extended to include extensive plastic flow.&apos; Thus, the shear-hardening coefficient, which is defined as the slope of the shear stress-shear curve, also is considered to be independent of orientation. It is noteworthy that deviations from this empirical shear-hardening law have been reported in cubic crystals whose initial orientation favors slip on more than two systems.&apos; Moreover, this law appears to have been derived from stress-strain data relating to relatively high values of shear strain (0.5 to 4), where widespread slip and complex distortions can be expected, regardless of crystal orientation. Since existing data indicate that the strain inhomogeneity in a crystal is manifested particularly in the early stages of flow, it would appear that a more exacting test as to the fundamental nature of the shear-hardening law would be to investigate systematically the shape of the stress-strain curve as a function of crystal orientation in the earlier stages of deformation. With regard to the general form of the shear stress-shear curve for cubic crystals, early studies show a parabolic hardening law, where the shear 1 stress is proportional to the square root of the shear-strain. Since this law was predicted theoretically by Taylor" in his original dislocation model for hard- ening, it has been accepted widely as a fundamental flow characteristic of cubic metals. However, it was recently pointed out by Masing6 hat the parabolic law is not the elementary form of hardening in cubic crystals, but instead is a consequence of complexities in the flow process (e. g., deformation bands and unpredicted secondary slip). Thus, in the very early stages of deformation (< 2 pct extension) where the occurrence of such complexities is unlikely, a different strain-hardening behavior might be anticipated. This view is supported by the recent work of Rosi and Mathewson7 on high purity aluminum where a linear law was obtained for extensions up to 2 pct. A linear hardening over a wider range of deformation also was reported by Rohm and Kochendorfer8 ho deformed aluminum crystals under conditions approximating pure shear. Even more pertinent is the recent evidence of Masing and Raffelsieper9 on high purity aluminum crystals. It was found that for crystals having initial orientations near a <l00> or <1ll> axis, a high hardening was obtained, whereas crystals with a <110> orientation exhibited a low and linear hardening curve followed by a region of more rapid hardening. Since much still remains obscure concerning the details of strain hardening as well as slip-band formation in face-centered-cubic crystals in the early stages of deformation, the present study was undertaken to evaluate the effect of crystal orientation on these two important manifestations of glide. It is important to note here that at the time of this study, Lucke and Lange11 presented information on the orientation-dependence of the shape of the strain-hardening curve in aluminum of various purities. Their work, which essentially represents an extension of that of Masing and Raffelsieper, in many respects is parallel to that of the present study. Experimental Procedure Production of Single Crystals: Single crystals of silver and copper of varying purity were used in

Jan 1, 1955

By S. J. Prison, C. R. Smith

The effect of fluid injection to control water coning in oil and gas wells was investigated. Analytical and model techniques were employed. The factors investigated were the position and length of the completion interval, the point of fluid injection, the viscosity of the injected fluid and the relative thickness of the oil and water sections. The resulting influence of these factors on the net producing water-oil ratio was determined. Several important conclusions can be drawn from the study. In general, it was found that the net producing water-oil ratio can be reduced by fluid injection. The magnitude of this reduction depended on the factors listed above. An important practical consideration is that the injection fluid may be either oil or water. If the injected fluid is less dense than the connate water of the reservoir, the fluid will not be lost. This fact is reassuring when valuable oil is being injected. Efforts to suppress water production were more successful when the injection fluid was more viscous than the reservoir oil, or when a zone of reduced permeability existed in the vicinity of the point of fluid injection. Under test conditions, little benefit was derived through the use of impermeable barriers or cement "pancakes". INTRODUCTION The occurrence of water coning has been known for at least 60 years. In thin oil or gas pay sections, the presence of an oil-water or gas-water contact hinders production and often causes early abandonment of the afflicted well if a completion is even attempted. Even when relatively thick pay sections are found, the encroachment of water when a water drive is present will eventually pose serious water coning problems. This water is often corrosive, expensive to separate from the oil or gas and is costly to dispose of. The theory of water coning has been discussed by a number of authors. 1,2,3,4 Briefly, water coning to the producing interval in a well is due to pressure gradients resulting from the production of fluid from the reservoir. These pressure gradients will cause a water cone to rise toward the bottom of the producing interval if a water-oil or water-gas contact exists. The tendency of the water to cone is offset or partially offset by gravity forces since the water has a higher specific gravity than the oil. A balance then exists between two forces, gravitational forces arising from the difference in specific gravities of the oil and water, and the pressure gradients causing the flow of fluids to the wellbore. If the pressure gradient exceeds the gravitational force, water coning to the wellbore occurs and water production results. Through the years considerable thought has been given to the water coning problem. More than 50 U. S. Patents have been granted to inventors on the subject. A relatively complete literature review of the water coning problem has been made. 5 A number of these patents hold considerable promise for the solution or the partial solution of the water and/or the coning problem. Very little has been written describing field tests of techniques for the suppression of water coning. A notable exception is the paperby West. 6 He reports success in reducing gas coning by a combination of gravel packing and oil injection above the oil-producing interval. He also describes a comparable method to prevent water coning, but provides no field examples. This study experimentally and analytically verifies the benefits of oil injection as a means of partially or completely suppressing the water cone. While the gas coning problem was not treated, it is anticipated that results comparable to those obtained in water suppression could be obtained with reduced oil injection since the viscosity contrast between oil and gas exceeds that between oil and water. For the purpose of this study, the conventional potential flow theory was applied to the water-coning problem. The experimental verification centered on both a radial and a linear model. The model study permitted the investigation of complex flow configurations and the use of fluids of differing densities and viscosities. No analytic expressions are available to permit a solution of the problem as stated (see Fig. 1).

By R. E. Delavault, H. V. Warren

In normal soils there are usually 10 to 50 parts of copper in every million parts of .soil. Only 0.2 to .5 pct of this copper can be found by any simple cold chemical attack. Now, with rubeanic mid reagent paper, a prospector or field geologist can detect as little us 4 ppm of readily available copper ill soil. This degree, of sensiticity is enough to determine the presence. of copper anamalous an as and, ecentually, to discouer copper mineralization. Circumstances determine whether it is better to make analyses in the field or in a permanent laboratory. The rubeanic acid test described in this article has been designed primarily for field use: it is simple and virtually foolproof, and it requires a minimum of field kit." It is sensitive, easily de- • Ed. Note: Persons Interested in purchasing kits suitable for rubeanic acid prospecting can obtain information by writing Eldrico Geophysical Sales Ltd., 633 Hornby Street. Vancouver 1, B.C. The University of British Columbia does not produce these kits for sale and has no financial interest in their production tecting 4 ppm of readily extractable copper in a soil. This is by no means a quantitative test, but it is accurate enough to provide a valuable indicator of copper anomalous areas for both prospectors and field geologists. The easiest method for detecting metal deposits that do not produce visible float or stains is to make a simple chemical test for the metal in overlying soil, or in the silt of a stream that may have picked up metal farther upstream. In Brief: Testing for copper may be done easily by shaking a soil sample with strong acetic solution in a small test tube and pouring the mud into a small filter, the tip of which rests upon a strip of reagent paper impregnated with rubeanic acid (di-thio-oxamide). When copper is present—and only when it is—a blue spot develops. The more copper, the darker the spot. If the copper content is merely the small amount present everywhere, there is a pale blue or hardly visible spot; if it is abnormally high, the spot will be dark. There are, of course, intermediate cases where the experienced geochemist cannot tell offhand whether a medium-strength spot represents rich agricultural soil, weak copper mineralization, or distant rich copper mineralization. Reagents and material are inexpensive; the test may be readily done on the spot with a simple kit easy to pack and handle. Anyone interested in general problems of soil sampling as applied to prospecting may refer to an article recently presented to the AIME. In exploration work it is the contrast between the metal content of anomalous and background areas that is important; absolute values become of greater interest when an anomalous area is being investigated in detail. With specific reference to copper, it has been the authors&apos; experience that the amounts of metal extracted from anomalous and normal soils with buffer solutions of decreasing pH show better contrast if an acid reagent is used. This contrast tends to increase with increasing acidity until 3 to 4 pH is reached. Using a short cold attack on unheated soil, it has been found that further increases in acidity do not produce better results, and only increase the hazards involved in carrying strong acids. An acidity of about pH 4 is satisfactory for direct determination of copper by dithizone. But dithizone itself introduces some problems: it must be made up fresh at frequent intervals, and with some soils, notably those with much ferric iron, oxidation mag take place before all the copper has reacted with the dithizone. Rubeanic acid keeps its strength unimpaired for long periods, is unaffected by oxidation, and is practically specific for copper at pH 4. Consequently it seems an ideal reagent to use in prospecting for copper. History and Background: Rubeanic acid (systematic name: dithio-oxamide (SC-NH2) has long been known as a spot test reagent for some heavy metals with which it gives a number of compounds. Only copper and some metals of the platinum family are believed capable of providing any ru-beanate compounds under conditions of moderate

Jan 1, 1959

By F. C. Pittman, D. W. Harriman, J. C. St. John

This paper mentions briefly the history of hydraulic jetting as applied to perforating and fracture initiation. It points out the advantages of hydraulic perforation and undercutting as an aid for creating a fracture at the point desired rather than depending upon the weakest point in the formation for breakdown. It describes early experimental work with jet nozzles in search of better nozzle materials. The effect of splash-back damage and its subsequent influence on jet body and tool design during this work is discussed. A series of cutting-rate curves for jets cutting steel and steel-cement-formation combinations is presented to show the effect of hydrostatic head and the point of diminishing returns with respect to cutting time. There is a series of photographs showing various types of rock formation in which perforation and undercutting tests were made. These stones were drilled and the casing cemented in place as in an actual well. The casing was perforated and circularly cut as if preparing for a fracturing job. The conclusion reached in the paper is that hydraulic jetting with sand-laden fluid can be used for perforating and undercutting casing, cement and formation rock for the intended purpose of inducing the formation to fracture at a desired point. INTRODUCTION Hydraulic jetting as a means of cleaning a formation during acidizing has been used for many years. The acid-jet gun was used to clean formation and for drilling cement from casing with acid. This tool was dropped to a seating ring installed on the tubing and could be retrieved by reverse circulation or wire line. In this process, the fluids were directed against the formation to clean and penetrate beyond the mud-damaged area. After the development of the hydraulic fracturing process, interest in jetting the formation with abrasive-laden fluid was renewed. The cutting action of abrasive fluid on pumping equipment, which is a well known problem, has been utilized to perforate and undercut casing, tubing and formation. In this process, surface areas are provided in the formation on which the frac- turing pressures may work to produce a fracture at the location desired. EQUIPMENT The tools used consist of bodies containing two, three or four jets in a single horizontal plane equally spaced around the circumference. The body is threaded to the end of a string of tubing and run into the well. In addition, an expendable tool is available that may be left in the hole after perforating and produced through until necessary to remove the tubing. The bottom of each tool is equipped with a ball-type back-pressure valve. The ball can be reversed to the surface and recovered. This allows reverse circulation so that loose sand which accumulated below the tool while jetting may be removed before the fracturing job. The present jetting tools are of such length that, when screwed together, the jets fall on 12-in. spacing. ANALYSIS OF THE PROBLEM Early work with nozzles indicated that hardened steel was not a suitable material for jets and that more durable material would be required. Ceramics were tried and found to be superior to steel but still too shortlived for most applications. Tungsten carbide, which was tried and found to be the best material available, is now being used for jet nozzles. Analysis of the problems presented by this process indicated that the following information was needed. 1. The effect of submergence on a jet stream and the effect of submergence on the cutting rate of a jet stream. 2. The cutting rate and depth of a jet stream in steel. 3. The cutting rate in various formations and point of diminishing returns. 4. Size of hole or slot cut in a pipe by a given jet. 5. Fluids and sands used. 6. The flow of various weight fluids through the jet nozzle and the discharge coefficients. 7. The type cut formed in the formation by the jet stream. 8. The stretch and contraction of tubing due to temperature and pressure. The cutting effect of a jet stream on a target in the atmosphere is rapid and spectacular as most of the