Search Documents

By William H. Baer, George M. Carlton, Blake M. Loring

IT is a well known fact that age-hardening alloys remain in a supersaturated, or partially supersaturated, condition only for limited periods of time at temperatures below the solvus. In order to develop optimum properties by subjecting the quenched alloy to precipitation or age-hardening treatment at a specified temperature, it is necessary that the cooling rate be sufficiently high to maintain the required degree of supersaturation of the solid solution. In practical applications the size and shape of the specimens obviously have considerable influence on the rate of cooling and there is need for more information on the effects of various rates of cooling. Cooling rates of quenched aluminum alloys generally have been established by the type of quenching medium, the temperature of the medium and the dimensions of the specimen.1,2,3 Except for the work of Roth3 little quantitative information is available on the measurement of cooling rates of aluminum alloys and the significance of the influence of various cooling rates upon the mechanical properties. The purpose of the present investigation was to study the use of the Jominy test for aluminum alloys (Table I). EXPERIMENTAL PROCEDURE The material for this investigation consisted of extruded rods 1 ¼ to 1 ½ in. in diam. The chemical compositions were as follows: [ ] The modified L-type Jominy specimen with dimensions shown in Fig I was selected as the most convenient means for obtaining a wide range of cooling rates. The standard Jominy specimen was not satisfactory because its cooling rate was not sufficiently high. The four flat surfaces machined at right angles along the length of the L-type specimen to a depth of 0-015 in. facilitated the hardness measurements. The specimens were machined from the extruded stock with no intermediate forging. New specimens were used for each aging experiment. The specimens were given solution treatments of 2 hr duration at recommended temperatures in a Hoskins furnace (Table 2). The temperature of the furnace was maintained constant to ±3°C. No protective atmosphere was necessary because the thin film of oxide that formed on the surface of the specimens had no effect on the hardness measurements.

Jan 1, 1948

By P. Bolsaitis, L. Skolnick

A model of metallic solutions is postulated which explains the energy of formation of alloys on the basis of changes in electron density around solute and solvent atoms and changes in pairwise interactions between atoms. The model is based on the Wigner-Seitz cell model of metals, with the electronegativities of the metals as the parameter for the electron-attracting power of the constituent atoms. In contrast to models based on the description of cohesive energy in terms of pairwise interactions only, which require an empirical, adjustable correction parameter to the Berthe-lot relations in order to predict negative energies of formation, the electron cell model accounts for both negative and positive energies on the basis of parameters of the pure components. Calculated heats of mixing based on published parameters of the pure metals are found to compare favorably to experimental values, despite the absence of any adjustable parameters in the model. THE formulation of an "exact" quantum mechanical model for the energy of cohesion of metals reduces ultimately to the many-body problem and for a complete solution would require the knowledge of wave functions and energy levels of all the particles in the system. The case of alloys is further complicated by the fact that the potential fields around the constituent atoms are different and the matching of boundary conditions in terms of the resulting wave functions is still an unresolved mathematical problem. It appears that in spite of the numerous investigations that have led to an elucidation of many properties of the metallic state, the formulation of the Hume-Rothery rules in 1931 marks the lone accomplishment toward simple, qualitative prediction of the energy of formation of alloys. More recently Friedel'' and Arafa have utilized the modern concepts of the electronic structure in metals in combination with the Hume-Rothery rules to arrive at quantitative estimates of the energy of formation of alloys with low solute contents. The relative success of the Hume-Rothery rules and Friedel's and Arafa's studies encouraged broaching the subject of formulation of a model based on realistic physical parameters and of conceptual and mathematical simplicity that could be applied to alloys regardless of concentration. On the basis of the free-electron theory, the cohesive energy of pure metals can be expressed as a function of "valence" (number of free electrons per atom), lattice parameter (or density), and the ioniza-tion energy. In addition to the electronic contributions to cohesion, one has to consider the pairwise exchange interaction energy between neighboring ion cores and the contribution from van der Waals forces. The energy changes upon alloying are viewed as resulting primarily from a redistribution of electron densities around the ions (a simplification of the more basic concept of a change of the wave functions of the electrons in the presence of a perturbing potential field). In addition there is a change in the pairwise interactions between neighboring ions which is usually the only factor taken into account in commonly used adaptations of the quasichemical theory. The electronegativities of the metals forming the alloy are used as the measure of the electron-attracting power of the ions in the alloy and the difference in electronegativities as the driving force for changes in electron energy on alloying. The interplay of pairwise interactions and electronic forces results in positive or negative energies of formation of alloys. Results obtained for systems to which the free electron model is best applicable are in good agreement with experimental values. 1) COHESIVE ENERGY OF METALS IN TERMS OF THE ELECTRON CELL MODEL The simplest physical model of a metal is that of a lattice of positive charges immersed in a sea of uniform, negative charge distribution represented by the

Jan 1, 1969

By Eric Jette

IN order to control a chemical process by other than empirical, rule of thumb methods, two types of knowledge concerning the reactions involved must be available: (1) the thermodynamics of the reactions, and (2), by no means less important for efficient operation, the mechanisms and kinetics of the reactions. Information on the thermodynamic side enables the operator to decide upon initial and final conditions, whether heat must be .added or removed from the system, whether the reactions proceed farthest in the desired direction at high pressure or low, etc. Knowledge of the mechanisms involves the determination of the individual steps by which an initial set of reactants, under given conditions, proceed to give the desired final products and kinetic studies upon which the mechanisms are based give the speed at which each of these reactions or steps take place. Thus thermodynamic studies of a 'reaction enable the operator to control the direction and extent to which the reaction can proceed, while kinetic studies enable him to control rates and thus the time' efficiency of the operations. The thermodynamics set the limit to which the reacting system approaches; the kinetics tell how fast the system actually approaches this limit. The two types of information are complementary and not antagonistic even though in discussing the mechanism the introduction of thermodynamics is entirely needless and generally of no assistance, while in thermodynamic studies mechanism need not even be mentioned.

Jan 1, 1931

By H. M. Beatty, T. L. Joseph, Gust Bitsianes

SUCCESSFUL blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blast- furnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO ? 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which C02 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature com- bustion of carbon above the tuyeres. Assuming that 1000 lb. of limestone is used per ton of pig iron, about 435 lb. of C02 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb. would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1942

Discussion of the paper of Robert Henry Lee, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2515 to 2522. J. E. JOHNSON, JR., New York, N. Y.:-This subject is of great and increasing importance, as the exhaustion of the deposits of ore of ideal character compels the iron industry to turn more and more to those which are less desirable on account of physical structure as well as analysis. Thus there has come about the use of the Mesabi ores in this country and also of the Minette ores in Europe, which produce far greater percentages of flue dust than did the lumpy ores first used. It is a matter of common knowledge that the utilization of this flue dust, containing commonly 50 per. cent. or more of metallic iron, has been a problem very difficult and tedious of solution. The number and variety of the solutions now offered is a sufficient proof of this. . I have no intention of going into the merits or demerits of any of these processes as such, but there are certain considerations concerning the effect of their product on the operation and fuel economy of the blast furnace which I believe to be new and which I desire to bring out. There are two methods, so different as almost to be direct opposites of each other, whereby an ore may exercise an unfavorable effect on the economy of the blast furnace. The first of these is well known and results from the ore being refractory and highly resistant to the action of the reducing gases of the blast furnace. This results in its being incompletely reduced when it reaches the zone of fusion and in the reduction being finished by the direct action of carbon in the lower portion of the furnace. This is so well understood as to need little elaboration or comment. There is, however, another action which may be equally as fatal to the economy of the furnace as the foregoing, and as this point is, to the best of my knowledge, not generally appreciated, it is one upon which I desire to lay particular stress. This consists in the ore being, in a sense, too reducible.

Jan 12, 1913

By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952

By T. F. Petty

Oil and gas production in North Central Texas has been found in sands and limestones in the Cisco, Canyon, Strawn and Bend series of Pennsylvanian age and in lime of pre-Pennsylvanian age. Production ranges in depth below the surface from 150 to 4500 ft.; a few wells have been drilled to depths in excess of 5500 ft. and penetrated rocks of pre-Cambrian age. In Table 1, the average depth of the pools is shown. No mention, however, is made in this table of approximately 30,000 bbl. of oil produced in Callahan County from a pre-Pennsylvanian pay, presumably the Ellenberger, and an excess of 1,000,000 bbl. of oil produced from limestone, which has been identified as Silurian in the south part of Young County. This well is being produced at the present time. In Table 1 a great many pools of minor importance are listed, which are merely productive spots, and throughout the various producing counties there are numerous similar spots, which might be listed as pools. Their production, however, is listed in the county totals. In Table 2, the totals of the oil wells, gas wells, and dry holes drilled before Jan. 1,1935, include only wells on which records are available to the writer. In Brown, Callahan and Shackelford counties 2924 very shallow wells (150 to 600 ft. deep) have been drilled, on which the record is not available. Possibly there are other wells that were drilled before the district was adequately scouted. No classification as to the depths of this total of 30,644 wells is available at present. Initially, nearly all the oil wells of North Central Texas produced gas, and several areas producing dry gas have been partly developed. A number of casinghead gasoline plants strip the gasoline from the gas produced with the oil, and the manufacture of carbon black is an important industry in Stephens County. Dry and residue gas are marketed through systems serving the various towns of the district, San Angelo to the southwest and the cities of Forth Worth and Dallas to the east. Considerable gas is used in repressuring several pools, the most important of which are the Stover of Brown County and the Cook of Shackelford County. During the past year, 32 gas wells were completed, adding a

Jan 1, 1935

By Gust Bitsianes, Joseph H. M. Beaty

Successful blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blastfurnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO - 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which CO2 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature corn bustion of carbon above the tuyeres. Assuming that 1000 Ib. of limestone is used per ton of pig iron, about 435 Ib. of CO2 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb, would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1943

By Joseph H. M. Beaty, Gust Bitsianes

Successful blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blastfurnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO - 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which CO2 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature corn bustion of carbon above the tuyeres. Assuming that 1000 Ib. of limestone is used per ton of pig iron, about 435 Ib. of CO2 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb, would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1943

By A. D. Schwope, L. R. Jackson, A. M. Hall

In the course of an extensive investigation of the comparative properties of several types of copper, data were obtained on the cold working and subsequent recovery and recrystallization of the copper. In this paper, relations between the degree of cold work and the course of re-crystallization are developed. In particular, it is shown that the course of recrystallization over long periods of time and at low temperatures can be predicted with reasonable accuracy from short-time high-temperature recrystallization data. Materials Used in The Investigation Three types of copper were used in this investigation; these were tough pitch, OFHC, and OFHC copper with 15 oz per ton of silver added identified herein as Lots C, D, and F, respectively. The material was supplied by the American Metal Co. Ltd., and processed by the Rome Cable Co. The analyses of the three types of copper are given in Table I. Originally, it started as wire bars 4 X 4 X 54 in. These bars were heated to 871° C in air and hot rolled to % in. rod. This rod was cold drawn to 0.204 in. rod (70 pct reduction) in three passes and annealed at 427°C for 4 hr. A portion of the 3/8 in. rod was saved for more detailed cold-drawing experiments. Starting with the annealed 0.204 in. rod, hard-drawn wires were produced by cold drawing to 0.081 in. wire in 7 passes (84.4 pct reduction in area). Half-hard wires were made by cold drawing the 0.204 in. rod to 0.102 in. wire, (75 pet reduction) in 6 passes and annealing at 427'C for 4 hr. This annealed wire was then drawn to 0.081 in. wire, (37.1 pet reduction) in 2 passes. Square rod was made by hot rolling wire bars to Re in. rod in 8 passes. This rod was then cold drawn to 0.445 in.-diam rod and annealed for 346 hr at 538°C. It was then cold drawn to 0.325 in. rod and again annealed at 538°Cf or 3 1/2 hr Hard square rods were then made by cold rolling this material to 0.257 X 0.257 in. rod, a reduction in area of 20.5 pct. Half-hard square rods were made by cold rolling to 0.268 x 0.268 in. square, annealing for 3 1/4 hr at 538°C and cold rolling to 0.257 x 0.257 in., a reduction of 8.5 pct. Soft wire or rod was made from all types of copper by annealing the hard-drawn material at 343°C for 3 hr in steam. The grain size of the annealed 0.081 in. wire varied slightly among the three lots: from o.o15+.oz5 mm in the silver-bearing OFHC to 0.035-0.045 mm in the OFHC copper. The annealed 0.257 in. wires were more uniform in grain size, averaging about 0.035-0.045 mm. Representative structures are shown in Fig I. Effect of Cold Drawing and Tensile Strain on Strength of Copper Conventional tensile tests were performed on the three types of copper in the various degrees of hardness described above. Results of these tests are tabulated in Table 2. The results in Table 2 are 6

Jan 1, 1949

By J. F. Butler

The degree and type of carbide dispersion resulting from changes in the cooling rate from austenite determine the amount of carbon remaining in solution after slow cooling- from a subsequent subcritical annealing treatment. A difjusion model has been proposecl to explain the effect of carbide dispersion on the amount of carbon retained in solution and the amount of carbon in solution has been related to the degree of carbon strain aging. COTTRELL and Leak' have shown that the rate of strain aging in low-carbon steels is dependent upon the amount of carbon and nitrogen in solution. Carbon can be effectively removed from solution as Fe , C by quench aging at temperatures of 200" C or lower; however, the relatively higher solubility of nitrogen at these temperatures prevents sufficient removal of nitrogen as iron nitrides. For this reason, nitrogen in solution has been considered the major cause of strain aging in rimming grades of commercial low-carbon steels. Nitrogen can be effectively removed from solution and nonaging steel produced through the addition of aluminum to form the stable nitride, AlN; however, the aluminum also causes deoxidation resulting in a killed steel. III an attempt to produce a rimmed steel which was also nonaging, Morgan and Shyne 2 investigated tile strain-aging properties of low-carban steels containing boron and found that strain aging was suplx-essed in steels containing as little as 0.007 pet B. The original purpose of this investigation was to determine the mechanism of strain-aging suppression by boron. Early in the study, the function of boron was discovered to be much like that of aluminum in that the formation of a nitride, BN, removed the nitrogen from solution.' However, during the course of the investigation, an effect of heat treatment upon the strain-aging properties and the amount of carbon in solution was found which could be related to the microstructure of the steel. The purpose of this paper is to examine these relationships among heat treatment, microstructure, carbon in solution, and strain aging in steels where nondetectable amounts of nitrogen are present in solution. EXPERIMENTAL PROCEDURE The investigation was carried out using 0.030 in. by 12. in wire specimens which had been cold swaged and drawn to the final diameter. Table I lists the compositions of the low-carbon steels used. Those with 'V' designations were vacuum melted and cast; the alloys designated 'AISI' were prepared from high-purity iron obtained from the American

Jan 1, 1962

By N. H. Emmons

THE work of a consulting engineer or manager, when controlling mining-operations, requires that he have all the information concerning the mine in as concise a form as possible, and as the ore-reserves and their depletion and enlargement are the vital points to be studied, it is well to have them kept up to date and in some convenient form. The present paper describes a method adopted by me, which shows in a very clear manner the ore-reserves in a mine. The case illustrated is that of a vein near enough to the vertical for the vertical elevation of the mine to be the main working-map. A flat ore-body would be represented on a similar plat, but instead of the horizontal thickness of the vein being shown in the circles, the vertical thickness would be inserted. Fig. 1 represents an ideal longitudinal elevation of a mine, plotted in the ordinary way, using 100-ft. blocks and section-lines. In a mine where the block-numbers are posted by the engineer underground, the system of keeping the ore-tonnages extracted from the different blocks is easily maintained, and the actual tonnages of ore extracted can be kept so that the surveyor can have a check on his estimate from time to time. The ore-reserve sheet, Fig. 2, should be the same size as the map it is to accompany. Each square is used for the description of the ore-reserve in the block it corresponds to on the elevation. Where the section-lines cross the levels a circle is drawn, in which are written the widths of ore at that point, these widths being used in the calculations of each block cornering in the circle. It has been found convenient to show the figures in black in the lower half of the circle when the actual widths of ore are known, and when it is necessary to make up the figures of probable ore, as at the time of making

Jun 1, 1912

By P. B. Crawford, W. L. Huskey

A study has been made to determine the effects of random vertical fractures existing in a reservoir matrix on the effective matrix properties and producing characteristics of a well. The study indicated that short vertical fractures may distort the isopotentials by 1 percent in the vicinity of the fracture. A correlation was developed which showed the effect of fracture density on the producing capacity of a well. The correlation indicated that fracture shape had little effect on producing capacity, but that total fracture length was closely correlated with the producing capacity. Effective values of reservoir permeability were found to correlate closely with fracture density when measured parallel to the direction of flow. INTRODUCTION In reviewing the petroleum literature, it is found that in most analytical solutions of hydrocarbon reservoir behavior the assumption is made that the rock is uniform throughout although core analysis and well logging surveys indicate that substantially all reservoirs are heterogeneous and some are fractured. Only in recent years have investigators studied the effects of reservoir hetrogeneity. Russell1 discussed the effect of fractures in reservoirs. The literature indicates that fractures greatly affect the exploitation of man reservoirs. This is described by Elkins and Skov2 and Little-field et al. 3 Several types of reservoir heterogeneity have been studied by unsteady-state methods. In 1959, Landrum et al. 4 showed that transient phenomena in hydrocarbon reservoirs could be studied by thermal models. pickering5 studied the flow of heat in stratified linear reservoirs consisting of plates of different metals separated by sheets of rubber which were suddenly exposed to a low-temperature source at one end. Cotman6 studied both laterally and vertically heterogeneous thermal model reservoirs with special reference to cross flow. Another type of reservoir heterogeneity involves the presence of highly permeable, circular lenses around or near the wellbore which was studied by Miesch7 using a thermal and a steady-state model. Many studies have been made of the effects of induced hydraulic fractures on well performance. 8-10 Work regarding vertical fractures that exist initially in the reservoir was reported by Givens, et al.11 Since there appears to be little published work on the importance and influence on reservoir performance of fractures that exist out in the rock matrix, this study was conducted to determine the effects of vertical fractures on pressure distribution, producing capacity and the effective permeability of the reservoir rock. The analogy between the flow of electrical current through a conducting body and the flow of fluid in a porous medium provides a convenient method of studying various aspects of petroleum reservoirs. For electrical radial steady-state flow,12 For steady-state fluid flow, With the above analogy, it is only necessary to establish the ratio of the values of the electrical units in terms of the corresponding flow units to make the analogy quantitative. The ratios are shown below.

By M. B. Kahle, A. D. Pernichele

Four types of slope failures in waste dumps are recognized debris flow, foundation failure, edge slump, and blowout. The first three types, although at times causing considerable damage to property and interfering with mine operations, are not usually dangerous to personnel because of their slow rate of movement. The fourth type, the blowout, is the most dangerous because of its explosive mode of failure and lack of forewarning. The December 1969 failure at Verona dump is presented as an example of a blowout. Data from piezometer holes indicate that the blowout was due to perched leach solutions near the face of the dump. The level of water in this zone is very closely related to the rate of leach water application on the dump. A detailed analysis of core samples indicates that the impounded water was perched on a zonal accumulation of jarosite which is associated with a buried dump surface. Drain holes proved successful in controlling perched leach solutions in the critical zone near the face of the dump. Monitoring of the water level in the perched zone is considered essential in preventing blowouts. The use of drain and piezometer holes has allowed an increase in the rate of water application on the dump while preventing additional failure.

Jan 1, 1972

By G. L. Oldright

DURING 1919, in the face of high cost for labor and supplies and a rapidly dropping copper market, the management of the Ohio Copper Co. of Utah was left with an orebody that had been shown to be very low grade, and a mill that could not make a satisfactory recovery, even by flotation, because a considerable proportion of the copper minerals was oxidized. About seven million tons had been mined by the use of a caving system, the best of the broken ore extracted and milled, and the nature and copper content of the rest of the orebody fairly well determined. The rock of the whole mine was shown to run between 0.3 and 1.3 per cent. in. copper. As, the Ohio Copper orebody lies at the contact of the original sandstone (now altered to quartzite) with the quartz monzonite intru-sion that was the source of the mineralization at Bingham Canon, the rock was thoroughly shattered. It was shown further that the rock was mostly quart-zite, with a few quartz-monzonite "fingers" projecting into it. Although some of the old cleavage planes had been healed by resilicification so as to leave some of the copper minerals disseminated in the rock, a large proportion of these minerals was distributed along the cleavage planes.

Jan 10, 1923

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By A. Bauer, P. Calder, N. H. Carr, G. R. Harris

Since both rotary and jet piercing drills are used by the Iron Ore Co. at Smallwood, it is often desirable in planning to know in which regions of the orebody or new orebodies a particular drill will be the most economic. This makes it necessary to establish a correlation between drillability and pierceability and some physical rock properties. For rotary drills a good correlation was found with penetration rate and grinding factor index. The jet piercers were found to have a reciprocal relationship in the sense that the best rotary ground was the worst jet ground and vice versa. It is also indicated how an economic comparison could be made using these penetration rate versus grinding factor index curves, the hole size distribution curves for single pass and chambered holes and the mine distribution curve for grinding factor index. A discussion is presented on the fuel oxygen ratios to be used in jet piercing and on the site gas sampling and analysis which has been used to set up the drills. The fuel has been cut back so that stoichio-metric conditions exist, carbon monoxide is drastically reduced and pop-up or exploding holes eliminated. No decrease in penetration rate has been observed contrary to the published results of previous workers. The blasting procedure and results at Smallwood are discussed and the operation of Iron Ore Co.'s slurry pump-mix truck is also described briefly. Smallwood mine is part of the Iron Ore Co.'s Carol Lake operation and is situated in Labrador, 240 miles north of Sept-Iles, Quebec. Last year 15 million tons of crude ore were crushed to yield 6.3 million tons of concentrate and pellets. This year the figures will be 17 million tons of crude and 7% million tons of concentrate and pellets which is the full plant capacity. Carol Lake ores consist primarily of specularite and magnetite mixed with quartz. For convenience the ore has been split-into the following classifications depending on the percentage of magnetics in the sample, shown in brackets: specularite (0 to 10%), specularite-magnetite (10 to 20%), magnetite- specularite (20 to 30%), magnetite (>30%). The order of classification also represents the order of increasing grinding difficulty - the specularite generally being the easiest and the magnetite the hardest. The orebody also contains a small percentage of waste materials consisting of limonite carbonate, quartz carbonate and quartz magnetite. The first two materials are among the softest in the mine, generally softer than the specularite, and the quartz magnetite is amongst the hardest. The bulk of the material in the mine is of the specularite-magnetite and magnetite-specularite classifications. As a result of test drilling at Smallwood in 1960 with rotary, jet and percussion drills, the Iron Ore Co. purchased four JPM-4 jet piercers for the bulk of production drilling and set up an oxygen plant to supply 20 tons of oxygen per day. This oxygen is sufficient for two machines operating full time and one part time. In addition, there are two 50-R, one 60-R and one 40-R machines in use. The benches are 45 ft high and 50 ft holes are generally drilled. JET DRILLING At the onset of jet drilling in the late fall of 1962, two major problems were encountered: 1) freezing due to winter operations; experience and the use of heat at more places, such as the rotary head, has eliminated this,'" and 2) exploding or "popping" drilled holes; this happened frequently (several holes "popping" each day) and was the cause of two lost time accidents. In one instance a hole was being measured with a tape which fell down the hole causing it to "pop." Safety glasses though pulverized saved the wearer's eyesight. Various methods were then employed to detonate the holes before measuring or loading (dropping lighted rags of fusees down, or sparking across a spark gap). These methods were time consuming and far from completely successful. Consideration was given to the fuel oxygen ratio on the machines and what this would produce in the way of product gases. A fuel oxygen weight ratio of 0.35 which was quite oxygen negative was being used. Theoretically appreciable carbon monoxide would be produced at this fuel oxygen ratio. On the close down procedure of the jet which calls for low oxygen after flame out, oxygen would be left in the hole along with this carbon monoxide. This is an explosive mixture. The fuel oxygen ratio was cut back to stoichiometric

Jan 1, 1967

By Carl F. Floe, Michael B. Bever

TRE solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to 1300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. REVIEW OF PREVIOUS WORK The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available. According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar6 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwas3é reported large hydrogen solubility values for several compositions of copper- tin alloys, which appear to be in error.

Jan 1, 1944

By David L. Holt

The contribution of grain boundary shear to total elongation, CS/E&apos;, has been measured in an Al-Zn eu-tectoid alloy that was quenched from above the invariant temperature, then annealed at 250° C to a grain size of&apos; 1.8 p. At 250°C, ks/E&apos; is low at both high and low strain rates, but reaches a maximum, estimated as 60 pct at an intermediate rate of 5 X 10 per rnin. Rate sensitivity, as measured by the index m = a log a/a log E&apos;, follows the same trend, and furthermore the maximum values of m and -cur at approximately the same strain rate. This result, combined with the metallographic observation that boundary migration enhances boundary shearing, is interpreted as supporting a previous suggestion that the high rate sensitivity characterizing super-plasticity is the result of combined boundary shearing and migration. It is suggested that the latter event relieves stress concentrations at triple points, and smoothes boundaries so that stress is governed largely by a viscous boundary shear. GrAIN boundary shear has been considered in relation to superplasticity in several recent papers.&apos; The problem has been to explain the high strain rate sensitivity of flow stress, and the variation of rate sensitivity with strain rate (E&apos;) and grain size (L). The requirements for superplasticity, small L and high T, suggest the reasonableness of an approach to high rate sensitivity involving grain boundary shear. Further support came from experiments on the A1-Cu eutectic alloy,&apos; where it was found that strain rate sensitivity of cast material annealed to produce an equiaxed, micron-size grain is always low; taking as an index of rate sensitivity m = a log a/a log <, m < 0.3. However, m in hot-worked alloy of comparable grain size can be as high as 0.7. In the cast and annealed material, each phase is a single crystal, the only boundaries are interphase boundaries, and it is, consequently, geometrically impossible for boundary shear to contribute to deformation in any major way. Other observations (for hot-worked material) were a-L at constant (low) strain rates and indications that the rate of recrystallization was enhanced as strain rate increased. As a result of this work, it was proposed that high rate sensitivity arises from a deformation mode of boundary shear associated with boundary migration. Migration serves to relieve stress concentrations at triple points, and smoothes boundaries so that they assume properties of fluid films. On the other hand, the low rate sensitivity observed at high and low strain rates reflects deformation of bulk material. Measurement of the variation of grain boundary shear with strain rate and m have not yet been made. Such measurements are important, especially in view of a proposal, differing in detail from the above, that high m arises merely from a transition between a grain boundary shear mode of deformation at low rates to a transgranular mode at high rates.2&apos;4 In the present work, the contribution of boundary shear to total deformation is measured and in addition metallographic observations are made on surfaces of deformed specimens to look at the interaction between boundary shear and migration. The Al-Zn eutectoid alloy was chosen for its homogeneous, fine-grained structure, which is obtained readily without hot-working. It has also been the subject of a previous phenom-enologically directed study. EXPERIMENTAL Material. Compression specimens, cross section 4 by + in., length \ in., were machined from a sand-cast ingot of composition 77.5 wt pct Zn, 22.5 wt pct Al. (The melt was prepared from 99.9 pct Zn and 99.99 pct Al.) After homogenization at 375°C for 50 hr, the specimens were quenched in brine and removed before the heat evolution that accompanies de -composition of the high-temperature phase.5&apos;6 The resulting microstructure, see Fig. l(a), was too fine for grain boundary sliding to be easily studied; coarser structures were obtained by annealing for various times at 2 50°C. Annealing was terminated by a brine quench. Final average intercept lengths between all grain boundaries (both interphase and those lying in a phase), L, were: 0.5 p [annealed for 15 min, Fig. (a)], 0.8, 1.1, and 1.8 p [Fig. l(b)l. Testing Procedure. An Instron machine was used for most of the compressive deformation. Tests were of two types: those in which crosshead velocity was changed in steps to measure m as a function of strain rate15 and tests at constant velocity to a fixed (engineering) strain of -0.2 (20 pct). Stress reached a steady-state value (a) which was plotted, on a logarithmic scale, against log strain rate (E&apos;). An alternate and equivalent evaluation of m was to take the slope of the log o vs log 6 curve. Time at temperature before testing was 15 min. Strain rates covered by the Instron (4 x lo-&apos; to 4 x 10&apos; per min) were insufficient; at a higher rate of 5 x lo2 per min a gas-operated testing machine was used, the gas driving a piston to compress the specimen at a controlled velocity.&apos; To obtain points on the log a vs log E&apos; curve at low rates, specimens were compressed by a dead weight. strain rate was an average value computed by dividing strain at the end of test by loading time. In some tests strain was measured at fractions of the loading time; creep rate was found to be reasonably constant.

Jan 1, 1969