Search Documents

By E. C. Wright

The bessemer process is nearly one hundred years old. William Kelly, the American inventor, was able to demonstrate that he had accomplished the pneumatic purification of molten pig iron as early as 1847; Henry Bessemer's English patent was granted in 1855. The application of this steelmaking process since then and the present position of bessemer steel are concisely discussed on pages 355 and 356 of the fifth edition of "The Making, Shaping and Treating of Steel." The great expansion of the automotive, machine-tool, chemical and oil industries after I9I0 opened up a large market for special steels, whereas the output of steel before that time was mainly for structural purposes. The need for building more blastfurnace capacity complementary to bessemer operations, combined with the availability of the' necessary amounts of steel scrap, both contributed to the extension of open-hearth plants at the -exense of besskmer capacity. The ability of the open-hearth furnaces to consume virtually all types of raw materials as far as phosphorus content is concerned, and the need for selecting low-phosphorus ores of rapidly decreasing sources for the bessemer, also played a part in the reduction of bessemer steelmaking operations and the increase in basic open-hearth plants. As a consequence, the proportion of bessemer steel made, in this country decreased from 65.7 per cent of the total in 1900 to 37.1 per cent in 1910, and only 6.8 per cent of the total in 1937. The metallurgical concepts existent between 1910 and 1920 caused the writing of many specifications of very low phosphorus and sulphur content, which definitely barred bessemer steel from many commodities. Now sulphur is being added to many open-hearth and bessemer steels in amounts far exceeding the maximum sulphur content of good bessemer steel. Re-phosphorizing is also widely practiced for several specific applications. Even today, the chemical-analysis limits of many important steel specifications have an arbitrary and archaic tinge. The old standard "0.30 to 0.60 per cent manganese" might be mentioned in this connection as similar to the rigid requirements for maximum sulphur and phosphorus that were established at least 25 years ago. The literature is full of vague and complee discussions of the effects of nitrogen and oxygen where these elements existed in steel in amounts less than 0.02 per cent. Many failures have been attributed to these elements without reasonable proof on which to base the conclusion. Methods of determining oxygen in steel require such complicated equipment that only a few research laboratories have the required apparatus. Even so, the accuracy of oxygen determinations in steel has been only recently reproducible. Up to the present time, no one has succeeded in obtaining a sample of molten steel that accurately indicates the full oxygen content of the metal in the furnace or ladle because the molten sample

Jan 1, 1944

By James M. Stapleton

IT has long been recognized by blast- furnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (I) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/C02 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/C02 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. APPARATUS The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943

By J. E. Ostberg, G. Phragmen, A. Hultgren, S. Wohlfahrt

Detailed study was made of a number of rimming ingots, both low and high carbon, and especially upon effects of superimposed air pressure. Requirement to suppress core bubbles is between 10 and 15 atm; at 6.5 atm freezing was in semikilled manner and at 3 atm, steel was of rising type. Probable mechanism of freezing under various conditions is discussed. AN earlier paper' reported an investigation made by a committee for studying rimming steel ingots appointed by Jernkontorets in Stockholm. The present paper is the outcome of some further work done by the same committee. Since the characteristics of ordinary rimming steel are connected closely .with the amount of gas liberated during freezing and since this amount of gas is governed by the pressure, it was considered of interest to ascertain in what manner and to what extent definite pressures applied to the top of the liquid steel in the mold would affect the solidification process and the consequent structure of a rimming steel of ordinary composition. The experiments were made at the Domnarfvets Steel Works. The steel was made according to normal practice in a 4-ton Rennerfelt electric furnace. Ferromanganese was added in the furnace; no aluminum was added, with one exception. Analyses of the four heats are given in Table I. The top-poured ingots measured about 12 in. sq x 48 in. and weighed about 1300 lb. One or two ingots of each heat were allowed to solidify under pressure, using a special device for admitting compressed air to the upper closed part of the mold, as shown in Fig. 1. A heavy plate sealed with asbestos was bolted to the top of the mold. The plate had a tapered aperture for pouring. Immediately after pouring the hole was closed by a wedged plug, and compressed air was admitted through a hole in the plug. Because of some delay in applying the plug, full pressure was not reached immediately. The pressure was adjusted to the desired value as indicated by a manometer. In order that the interior of the ingot might have the benefit of the pressure, the freezing of the top crust was delayed by a refractory lining applied to the top part of the mold, Fig. 1. Ingots were also cast from each heat without applied pressure, and with and without refractory lining at the top. Axial sections of ingots were cut either of the whole ingot or of some part of it of special interest; sections were polished and usually etched.' To facilitate description of structures the following terms may be used for different types of ingots solidified under gas evolution: 1. Box-hat or boot-leg ingot: Abundant gas evolution during casting and during rimming; no rim holes. 2. Normal rimming ingot: Lively gas evolution during rimming; usually rim holes in lowest part of

Jan 1, 1952

By Paul L. Burkhart

THOUGH at an earlier period brief studies had been made by the Lehigh Navigation Coal Company Inc., it was not until 1924 that J. B. Warriner, then general manager, called for a comprehensive study of timber treatment, treating solutions, and related operations. Because of the impossibility of procuring accurate costs and other pertinent treating data, the American Wood Preserving Co. agreed to treat a car of mine timber at the Port Reading plant of the Reading Railroad. Fig. I shows the treating data collected at the treating plant on this timber, which was installed in two of the Lehigh mines in 1925. Table i.—Results of Timber Survey in 1925 before Treated Timber Was Introduced Length of tunnels and gangways ft..... 522,987a Length of tunnels and gangways timbered, ft.................................. 224.880 Number of steel mine sets in use......... 2,412 Number of timber sets in use............ 63,834 Number of timber sets with evidence of rot 50: 419 Number of timber sets with evidence of squeeze..... ...................... I3,415 Percentage of all timber sets showing evidence of failure: BY wet rot........................ 6.0 By dry rot........................ 73.0 By squeeze....................... : Average life of wood set in Panther Valley, years............................... 5.3 • 99.05 miles. In the latter part of 1925, a survey of the tunnels and gangways of the company's Panther Valley mines was made to determine the proportion of gangways or tunnels timbered, cause of timber failures, approximate life of the average wood set and the approximate percentage of treated timber that it would be profitable for the company to use. Results of this survey appear in Table I. Because of the high percentage of timber that gave evidence of failure by rot, as noted in Table I, and a further study of the life of the sections where timbering was necessary, it was deemed advisable to fill 25 per cent of the yearly gangway timber requirement with treated timber. Quantities and Treatments OF Treated Timber Purchased In the early days of the program, none of the large treating companies would accept orders for small quantities of treated timber and the company was compelled to state the quantity of timber it would require at each operation in each month of the year. Table 2 is an example of the tabulation given to the various treating companies to assist them in making a yearly bid on the minimum quantity of timber required by the company during the year 1931. A bill of timber was calculated for each car, the weight of which would be between the minimum and maximum weight permitted for railroad-car loading. The treating company was paid for timber upon delivery at the operation specified. As extra cars of timber were required, they were ordered from the treating company, and payment was required On their receipt, on the basis of the piece or tonnage

Jan 1, 1942

By Paul L. Burkhart

THOUGH at an earlier period brief studies had been made by the Lehigh Navigation Coal Company Inc., it was not until 1924 that J. B. Warriner, then general manager, called for a comprehensive study of timber treatment, treating solutions, and related operations. Because of the impossibility of procuring accurate costs and other pertinent treating data, the American Wood Preserving Co. agreed to treat a car of mine timber at the Port Reading plant of the Reading Railroad. Fig. I shows the treating data collected at the treating plant on this timber, which was installed in two of the Lehigh mines in 1925. Table i.—Results of Timber Survey in 1925 before Treated Timber Was Introduced Length of tunnels and gangways ft..... 522,987a Length of tunnels and gangways timbered, ft.................................. 224.880 Number of steel mine sets in use......... 2,412 Number of timber sets in use............ 63,834 Number of timber sets with evidence of rot 50: 419 Number of timber sets with evidence of squeeze..... ...................... I3,415 Percentage of all timber sets showing evidence of failure: BY wet rot........................ 6.0 By dry rot........................ 73.0 By squeeze....................... : Average life of wood set in Panther Valley, years............................... 5.3 • 99.05 miles. In the latter part of 1925, a survey of the tunnels and gangways of the company's Panther Valley mines was made to determine the proportion of gangways or tunnels timbered, cause of timber failures, approximate life of the average wood set and the approximate percentage of treated timber that it would be profitable for the company to use. Results of this survey appear in Table I. Because of the high percentage of timber that gave evidence of failure by rot, as noted in Table I, and a further study of the life of the sections where timbering was necessary, it was deemed advisable to fill 25 per cent of the yearly gangway timber requirement with treated timber. Quantities and Treatments OF Treated Timber Purchased In the early days of the program, none of the large treating companies would accept orders for small quantities of treated timber and the company was compelled to state the quantity of timber it would require at each operation in each month of the year. Table 2 is an example of the tabulation given to the various treating companies to assist them in making a yearly bid on the minimum quantity of timber required by the company during the year 1931. A bill of timber was calculated for each car, the weight of which would be between the minimum and maximum weight permitted for railroad-car loading. The treating company was paid for timber upon delivery at the operation specified. As extra cars of timber were required, they were ordered from the treating company, and payment was required On their receipt, on the basis of the piece or tonnage

Jan 1, 1942

By K. O. Stamm, B. A. Rogers

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By B. A. Rogers, K. O. Stamm

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By H. T. Bowman

FOR more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the 1860's it was recognized that the process would benefit by some type of instrumental control.1 However, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower's eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham3' A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient monoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. CARBON-FEO RELATIONSHIP In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by McCutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a different method than were those

Jan 1, 1942

By J. K. Edgar

FOR a number of years the production and use of super-purity aluminum (better than 99.99 pct) has been steadily increasing. High-grade lots of such aluminum show certain outstanding characteristics not found in lower grades containing principally silicon, iron and copper as impurities. One such characteristic is the so-called "self annealing," that is, the recrystallization of the heavily cold worked metal at room temperature.' Interest therefore is aroused as to the effects of the impurities. It is well known that the amounts of silicon and copper which occur in aluminum of better than 99.95 pct are completely soluble, at least at elevated temperatures (above 200°C). Iron, on the other hand, is known to be fairly insoluble in solid aluminum. Thus, a knowledge of the limits of this solubility would be of considerable use in studying the characteristics of the high purity metal. All investigators have agreed that iron has very low solubility in solid aluminum. Rosenhain, Archbutt and Hanson2 reported traces of an aluminum-iron phase in the "purest samples of aluminum obtainable." Gwyer and Phillips3 reported that an iron constituent was visible under the microscope in metal containing ".0088 per cent iron." Roth1 found that in the solid state the solubility of iron in high purity aluminum was 0.01, 0.01, 0.017 and 0.022 pct at 225, 320, 500 and 600°C respectively. Dix5 working with alloys containing less than 0.03 pct impurities, concluded from microscopic and chemical analyses of eutectic areas that the eutectic composition was close to 1.7 pct iron. Dix placed the eutectic temperature at 655°C'. Archer and Fink,6 using high purity aluminum-iron alloys, found that the hypoeutectic liquidus intersects the eutectic horizontal at 1.7 pct. This is in fair agreement with the investigation of the aluminum-iron system by Gwyer and Phillips who placed the eutectic at 1.89 pct iron with a freezing point of 653° PREPARATION AND CHEMICAL ANALYSIS OF ALLOYS Electrolytically refined aluminum (99.991 pct aluminum) and a high purity aluminum-iron alloy (11.45 pct iron) were used in the preparation of the alloys for this investigation. To aid in controlling the iron content of the experimental alloys, an alloy of lower iron content was prepared first from these materials. The high purity aluminum was melted and heated to about 700°C in a plumbago crucible coated with alundum cement and the aluminum-iron alloy was then added. The alloy was thoroughly stirred, fluxed and skimmed and then chill-cast into notch bars. The analyses of the three materials are given in Table I. The alloys for the determination of the solid solubility of iron in aluminum were prepared by melting 600 g total of the aluminum plus the required quantity of the aluminum-iron alloy (No. 92531). These

Jan 1, 1948

By R. W. Smashey, B. J. Piearcey

The structure, composition, and morphology of the carbide phases present in the nickel-base superalloy, Mar-M200, hare been determined and three carbide phases observed. The MC carbide is a solidification product, and the M23 Co and M6C carbides are both prod~icts of solid-state precipitation. The identity of each phase usas determined by both X-ray and electron-diffraction techn~ques. Compositions of all three carbides were studied using the electron beam micro-probe analyzer and by unalyszs of electrolytically extracted residues. Optical and electron microscopy were employed in order that the time/temperature -dependent behavior of the carbides might be observed. Supplementary studies were completed on thin foils and oriented single crystals to determine the mor-phology and orientation relationship of each phase with that of the matrix. MAR-M~OO* is a high-temperature, creep-resistant superalloy designed for use in the as-cast condition. The "as-cast" microstructure consists of a solid-solution matrix, referred to as gamma (y), which contains a general, coherent precipitate of the inter-metallic Ni3(A1,Ti) referred to as gamma prime (?). As a result of dendritic segregation during solidification, a degenerate, spherulitic ? -?' eutectic constituent is present at the grain boundaries and the in-terdendritic regions, which is nucleated by the y on the dendrite tips. A primary carbide phase, a solidification product, is also present at the grain boundaries and in the interdendritic areas, and an additional carbide appears at the grain boundaries as a fine discontinuous precipitate. The alloy is particularly susceptible to heat treatment. For example, the mechanical properties of the columnar grained mater- ial are substantially improved by solution heat treatment, followed by an intermediate temperature age. Metallographic examination of heat-treated material reveals, however, that exposure to elevated temperatures has a marked effect on the microstructure of the alloy; in particular, it is observed that precipitation of considerable amounts of various carbide phases occur. The following investigation was carried out to determine the morphology, composition, and behavior of the carbides in Mar-Ma00 as an aid to the determination of their effect on the mechanical properties and stability of the alloy. THE PRIMARY MC CARBIDE The MC carbide phase appears in the interdendritic interstices and the grain boundaries. In directionally solidified Mar-M200 the carbide appears as very small particles in the chilled region, Fig. l(a), whereas in material less affected by the chill, it becomes larger and develops a dendritic morphology, Fig. 1(b). Step polishing of metallographic specimens from this region shows that in directionally solidified material the individual carbide dendrites are connected in a dendritic network within the metallic interdendritic interstices, whereas in material from the chilled region and in conventional Mar-M200 they are discontinuous, isolated dendrites. No orientation relationship exists between the primary carbide and the matrix.

Jan 1, 1968

By B. H. Cody

THE Morenci concentrator of the Phelps Dodge Corporation is a part of the project that was completed after five years had been spent in development of the open-pit mine, equipment and process testing in the former No. 6 concentrator, and construction of the reduction works. The reduction works, of which the concentrator is a part, is about a mile and a quarter southeast of Morenci, on the highway that leads up Morenci Canyon. The concentrator has a nominal capacity for the treatment of 45,000 tons of ore daily. The original plant, which has a rated capacity of 25,000 tons of ore daily and is now in its fifth year of operation, began production on Jan. 30, 1942. The addition, to increase the capacity 8o pct, began operation on Dec. 1, 1943. The equipment of the original plant has been described in MINING AND METALLURGY (May 1942). No changes in equipment were recommended for installation in the concentrator extension and only one major change, forced by a shortage of maintenance labor, has since been made. Metallurgical treatment has been altered in some ways as experiments progressed and as labor and economic conditions dictated. No complete description of the operation of the concentrator has been published, so this paper will record such operating and equipment changes as have been necessary, the operating methods that have been developed and the metallurgical results that have been obtained. Descriptions are given in the order of the processes with a flowsheet and an equipment list of each process for convenient reference. The questions asked by engineer visitors have guided the detail in which operation and maintenance are described. During the period Jan. 30, 1942 to Sept. 1, 1946, ore milled has totaled 43,595,253 dry tons, from which 1,643,885 tons of concentrate have been made, containing an indicated production of 783,164,809 lb of copper. The principal results obtained in operation of the concentrator during the years 1942 to 1945, inclusive, and to Sept. 1, 1946 are shown in Table 1. A graphic general flowsheet of the plant is given in Fig I. ORE The Morenci ore that is now being treated is a medium-hard monzonite porphyry in which the principal sulphide minerals are chalcocite and pyrite. A minor amount of covellite is present. Chalcopyrite and bornite have been observed under the microscope. The chalcocite occurs mainly as a coating on pyrite. Some of the coatings are so thick that the pyrite presents the appearance of being an inclusion in chalcocite. Some are less than one micron thick and are barely visible at 500 diameters magnification of a polished cross section. Some chalcocite is present as a dissemination in the gangue. Various oxidized copper minerals are present as a result of oxidation in place but they represent a minor proportion of the copper minerals of the ore body. Oxidation

Jan 1, 1947

By David B. Burrows, Rlkl Kobayashi, Norman L. Carr

The viscosity of hydrocarbon mixtures, whether in the gas or liquid phase, is a function of pressure, temperature, and phase composition. This paper presents methods for the prediction of the viscosity of the gas or less dense fluid phase over the practical range of pressure, temperature, and phase compositions encountered in surface and subsurface petroleum production operations. The correlation necessary to predict the effect of pressure on viscosities is presented in Part I. Serious discrepancies in high pressure gas viscosity data in the literature are discussed. The application of the correlation to predict absolute viscosities is discussed in Part 11. Auxiliary correlations are presented to enable calculations of viscosities from a knowledge of the pressure, temperature, and gravity of the gas phase. INTRODUCTION A knowledge of the viscosity of hydrocarbon fluids is needed to study the dynamical or flow behavior of these mixtures through pipes, porous media, or more generally wherever transport of momentum occurs in fluid motion. Since flow is predominantly in the laminar region in petroleum reservoirs, the influence of fluid viscosity on this flow is especially important. As early as 1894, Onnes1 and Onnes and de Haas' noted that the viscosities of homologs under corresponding states could be correlated. The theorem of corresponding states has been further developed and applied to the viscosity of pure, nonpolar gases under pressure by Comings, Mayland, and Egly.3 It was demonstrated that the viscosity ratio could be expressed rather closely as a function of reduced pressures and temperatures, 1.e.: µ/µ1 = f( TR2 PR) ........(1) temperature, absolute units where: TR =------------------------------ ------ critical temperature. absolute units _pressure, absolute units critical pressure, absolute units µ = viscosity of gas at reduced temperature TR and reduced pressure PR µ1 =. viscosity of gas at atmospheric pressure and at temperature TR Serious discrepancies in the viscosity of pure hydrocarbon gases at high pressures have been called to Our attention by Comings, and and Egly. They made a careful analysis of the following methods commonly used to measure gas viscosities: 1. Oscillating disc viscometer4,5 2. Rolling ball viscometer6,7 3. Capillary tube viscometer12 On the basis of their analysis of the problem and their experimental data on the viscosities of methane, ethylene, carbon dioxide, and propane, they preferentially selected data obtained by the capillary tube viscometer to develop their viscosity correlation. Since then a need has existed to verify the experimental technique of Comings, Mayland, and Egly for the determination of viscosities at high pressure; to extend the data to mixtures of hydrocarbons; and to extend the range of their correlation to include higher pressures. Using the correlation procedure of Comings, May-land, and Egly, the prediction of gas viscosities is resolved into the correlation of the effect of pressure, temperature, and composition on the viscosity of hydrocarbons and their mixtures and the prediction of viscosities of mixtures of hydrocarbons and other natural gas components at one atmosphere pressure.

Jan 1, 1955

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

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

Jan 1, 1942

By Morris Muskat

The detailed analogy between flow systems in porous media and the corresponding poten-tiometric model systems is developed under conditions where it may be desirable to take into account variable pay thickness, variable porosity, and permeability, and also the dependence of the fluid density on pressure. It is shown that in such models it is only necessary that the electrolyte thickness be made everywhere proportional to the millidarcy-feet of the formation. In contrast to the iso-vol type model, previously suggested as a basis for the analogy, the porosity does not enter directly in the construction of the model. It is introduced only in translating the electrical voltage gradient measurements into the equivalent fluid travel times. A discussion of this procedure is given. I NTRODUCTION It is now some 50 years since it was pointed out' that on the basis of Darcy's law Laplace's equation must govern the steady state flow of homogeneous fluids through porous media. It is 16 years since the obvious implication of this fact, namely, that such steady state homogeneous flow systems in porous media could be simulated by electrical analogies, was first applied2 to problems of practical interest with respect to oil production. In these initial studies major emphasis was placed on the use of electrolytic models, made of blotting paper, to give a direct and graphic history of the fluid particle motion in regular and infinite well networks. However, it was also noted there that the basic requirement of the model was that it give a potential distribution similar to the pressure distribution in the flow system, and that from the electrical measurement of the potential distribution the fluid particle motion could be graphically or numerically determined. This was demonstrated by application to the five-spot infinite network, for which a conducting metallic sheet was used to establish the equipotential contours. As anticipated, the fluid particle motion computed from these contours agreed well with that given directly by the blotting paper model. For irregular well distributions it was found more convenient to use electrolytic bath analogs rather than metallic sheets. Several investigations,3'4 as applied specifically to cycling well patterns, have been reported with these models, which have become known as "potentiometric models." However, the extremely laborious nature of both the electrical measurements by direct probing and the associated interprctive computations retarded the widespread use of these procedures. The electrical measurements can be accelerated by using a four-probe electrodc,5,6 which provides a means for simultaneously determining the streamline paths along which the fluid particles must move and the voltage gradients along these paths which are proportional to the fluid velocitics. With the increasing frequency of discovery of condensate pools, as drilling depths are becoming greater, the applicability of the potentiometric model to production problems, and especially to the study of well patterns for cycling, has been given a fresh impetus. Although the formal theory for determining the motion of fluid particles in porous

Jan 1, 1949

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946

By Carlton Beal

This paper presents useful charts for conversion of various viscosimeter units into centipoises and graphically summarizes published investigations of the viscosity of air, water and natural gas at high temperatures and pressures. Where possible, charts and correlations were constructed to cover a range of temperature (60°F. to 300°F.) and pressure (14.7 lb. per sq. in. abs. to 8000 lb. per sq. in. gauge) encountered in oil fields. Correlation charts, for the purpose of predicting crude oil viscosity and solubility behavior at oil field temperatures and pressures, were constructed from an analysis and correlation of 1332 viscosity and solubility observations from 953 crude oil samples taken from 747 oil fields. Of these fields, 501 are in the United States, including 75 in California. Of the 1332 observations, 1215 were viscosity values, including 786 of gas-free crude oil, 351 of oil saturated with gas, and 78 under-saturated with gas at pressures above the bubble point. Results show that crude oil viscosity at various reservoir conditions can be predicted with average deviations varying from 24.2 per cent for gas-free crude oil to as little as 2.7 per cent for undersaturated crude oil "above the bubble point." The solubility of crude oil may be predicted from oil gravity and saturation pressure with an average deviation of 22.0 per cent from observed values. In conclusion, it is shown that the viscosity of a gas and gas-saturated crude oil may be predicted within the accuracy of most reservoir computations. Viscosity is a measure of flow resistance; common units are in centipoises (cp.). The object of this report is to present conversion charts and simplified 'correlation charts showing the viscosity behavior of air, water, gas and crude oil and gas-saturated crude oil under oil field temperatures and pressures, which have been known to be as high as 300°F. and 8000 Ib. per sq. in. gauge under subsurface conditions. The viscosity of a liquid or gas is important because it is a measure of its fluidity, or its ability to flow through pipe lines or oil sands. Viscosity of air has become important because it is being used in secondaryl,2 recovery projects. The viscosity of natural gas and water at reservoir conditions is useful because they are almost universally associated and produced with crude oil. The viscosity of gas-saturated crude oil at reservoir pressures and tem peratures is of particular value in making estimates of oil reserves3 and rate of oil recovery from flush pools when production decline data are limited. Instruments Used to MeasuRe Viscosity There are many types of viscosimeters,4 and the instruments most commonly used to measure the atmospheric viscosity of liquids at moderate temperatures and their practical working ranges have been deScribed5,6 in detail. Fig. I and Fig. 2 are viscosity conversion charts which have

Jan 1, 1946

By S. R. Goodman, Hsun Hu

The rolling texture transition in copper as a function of deformation temperature is found to be quite similar to that in high-purity silver. The ordinary copper type texture changes gradually to the brass type, accompanied by an increase in the stacking fault frequency, as the temperature of deformation decreases. The rolling textures obtained at low temperatures and the corresponding annealing textures compare remarkably well with the ordinary rolling and annealing textures of low-zinc brasses. Furthermore, it is also found that the observed stacking fault energies of copper specimens deformed at low temperatures correspond closely with those of low-zinc brasses, as deduced from measurements of the dislocation nodes. These results are consistent with the idea that texture transition may be significantly dependent on the stacking fault energy. It was shown in a series of previous publications1"3 that the rolling texture of high-purity silver changes gradually from the common silver type (or the brass type) to the copper type* with increasing temperature *The silver or brass type rolling textures are commonly described as (110)[112],4,5 whereas the copper type rolling textures are mainly (123) [a121 and (146)[211].5 Other ideal orientations have been used by various investigators for the copper type rolling textures, but the actual difference among these ideal orientations is rather small. of deformation, and that such texture transition can be correlated with the change in stacking fault frequency as a function of rolling temperature. Furthermore, it was shown that the formation of annealing textures in high-purity silver from the various rolling textures obtained during the course of texture transition depends entirely upon the deformation texture. From a common silver type or brass type rolling texture (such as produced by rolling at 0" or at 50° C) the recrystallization texture is mainly (120)[211], which is quite different from the recrystallization texture of brass.* However, for both ma- terials the orientation relationship between the rolling texture and the recrystallization texture can be expressed in terms of similar rotations around [Ill.] axes of approximately 30 or 35 deg. They differ in that the [Ill] rotational axes are different. In the case of high-purity silver, the axes of rotation are the two (111) poles near the plane normal of the deformed specimen with a (11l)[112] type rolling texture, whereas in brass, they are the (111) poles near the direction of rolling. For high-purity silver with a predominantly copper type rolling texture (such as produced by rolling at 150° or 200°C) the recrystallization texture is mainly (100)[001], or the cube texture, plus its twin orientations. It was shown previously6 that such reorientation observed in copper or aluminum can be described as [Ill] rotations of 30 to 40 deg. For intermediate cases, i.e., when the rolling textures are composed of a

Jan 1, 1963

By Stephen Royce

[Stephen Royce.. I .......................... E. S. Moore.. 9 .......................... E. L. Bruce.. 10 ......................... J. E. Hawley.. 11 ........................ L. M. Scofield.. I 2] STEPHEN ROYCE, * Crystal Falls, Mich.Having examined and reported upon the Steep Rock Lake property and vicinity on several occasions for clients, and having kept in touch with the operation from 1938 on, the writer offers the following discussion of the valuable paper by Messrs. Roberts and Bartley, which was so kindly prepared in response to the writer's earnest request, made as a member of the Committee on Mining Geology. ORIGIN OF THE ORES The writer wishes to express complete agreement with the authors that the origin of these deposits was replacement action by hot ascending sulphide solutions of igneous origin, gaining access via the limestone and dolomite breccia channels, and acting mainly to replace the dolomite and limestone breccia with hematite and hydrated hematite. Some replacement in adjoining greenstones and tuffs by the same solutions may also have taken place, but the latter occurrences may represent replaced iron formations originally bedded in with the volcanics. Iron formation in the same relationship to volcanics is extensively developed on the western Menominee Range of Michigan, in the Middle Huronian belts; also appears in similar relations on the Vermilion Range; and is abundantly exposed in the same stratigraphic position no farther away than the southeast arm of Steep Rock Lake itself. Furthermore, the writer's classification of drill cores, made June 11, 1938, on the prop¬erty, contains the following, for hole 8, in the original strike of the A ore body: "332-342 ore; 342-350 much-leached sugary chert with thin ferruginous slate bands." This is a typical iron formation. The ore in this first group of holes (Numbers 6 to 13, incl.) is described in the writer's 1938 notes as follows: "The ore is hard, massive hematite with some limonite, and shot through with many small vugs." The breccia forms in the float ore and in the drill samples were also noted. As a field classification this does not check badly with Professor Schwartz's microscopic work. Notes supplied by Mr. Neeland, then geologist at the exploration, show: "Hole 23 has some iron formation, not logged yet." It appears therefore that there is some iron formation at the exploration, much iron formation in similar stratigraphic position in the vicinity, and iron formation similarly located as to volcanics on the Vermilion and western Menominee Ranges. Certain of the holes, notably Holes 25 and 27, showed some specular hematites resembling those known to be formed from cherty iron formation elsewhere. Hence the writer concludes that at least a small part of the Steep Rock ores results from replacement of iron formation. By far the greater part of it is, as the authors say, clearly a replaced limestone and dolomite breccia, with the breccia outlines still preserved in much of the ore, and all of the replacement is by hot ascending waters. The authors' citation of the neighboring Atikokan pyrite, pyrrhotite and magnetite

Jan 1, 1943

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675' and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675' and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946