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By Arthur E. Granger

IN the early days of the science, and until the recent past, geologists worked as individuals or in small groups. Prior to 1930 perhaps the largest single group under one administrative head was the Geologic Branch (now Division) of the U. S. Geological Survey, which employed at that time (including temporary help) 100 to 150 geologists. Today that same unit employs some 1500. In industry some companies employ as many as 100 geologists in a single department. These numbers obviously pose a need for administration. The basic qualifications for good administration are the same for any group of human beings, but the administration of geologists presents some special problems. Choosing Administrative Personnel: There are two kinds of personnel needs: 1) technical, which requires professional geologists who have proved their capabilities in the field, and 2) clerical and fiscal, which provide the necessary supporting or housekeeping functions. This discussion will be concerned only with the first category, except to point out the need for competent and understanding help from clerical and fiscal people and close relationship between top administration, technical or professional personnel, and the clerical and fiscal groups.

Jan 7, 1957

By R. W. Kraft, L. D. Graham

The process of' spheroidization, or more properly coarsening, of Al-CuAl,eutectic alloy specimens with various initial microstructures was studied by quantitative metallographic and X-ray diffraction techniques. By measuring the rale at which specimens with a very fine dispersion of phases (produced by quenching molten droplets of the alloy in water) coarsened it uias determined that the rate-controlling mechanism for coarsening was diffusion, probably of aluminum in the aluminum-rich phase. The lamellae in specimens with a high degree of microstructural and cr-ystallog/uphic anisotropy (produced hy unidirectional solidification of ingots) thickened during heat treatment by recession of the CuAl, platelets from jaulted regzons, yet the specinlens retained a very high degree of. anisotropy after prolonged heat treatments at a temperature within 8°C of the eutectic temperature. In such specimens the crystallographic orientation relationship between the phases remained constant and no change in the crystallographic substructure occurred. Based on these observations a model was developed for the coarsening—or rate of' thicken-ing—oj- the lamellar structures which predicts that the rate of decrease of interface area is proportional to the square of lamellar interface area. Experiments with degenerate and very coarse lamellar microstruc -tures preduced by extremely slow unidirectional solidification) indicate that initial microstructure is a most important factor governing the final micro-structure after heat treatment. The particle size and shape of dispersed phases are important parameters affecting the properties of a wide variety of two-phase materials. As is well-known, varietythe dispersed-phase particles tend to coarsen at appropriately high temperatures because the interface energy of the system is reduced by the concomitant reduction in interface area. The phenomenon of

Jan 1, 1967

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

By John Chipman, Karl L. Fetters

Tax relationship between the composition of the slag and that of the underlying metal during the refining of a heat of liquid steel may best be studied in the light of the two broad physicochemical concepts of equilibrium and reaction rate. Actual steelmaking processes, typified by basic open-hearth practice, involve such complexities of operating variables that it is impossible to distinguish with any degree of certainty between the general limiting conditions imposed by chemical equilibrium and the effects associated with rates of diffusion or of chemical reaction. Further advances in the physical chemistry of steelmaking will depend upon our ability to distinguish clearly between these two kinds of effects, and the experimental work that must be done falls naturally into two classifications. The first is the study of chemical equilibrium that cannot be carried out with assurance under operating conditions but must be done in the laboratory. The second is the subject of rates of reaction and diffusion and the mechanism of the process as a whole, which can best be studied under operating conditions. The latter is not entirely independent of the former, since its interpretation often requires a knowledge of the equilibrium state. It is the purpose of this and of several papers that will follow to present the results of laboratory investigations of equilibria involving liquid steel and slag. Open-hearth slag is a complex mixture containing at least eight major components and perhaps twice as many whose influence may be classified as probably minor. It is not surprising that progress toward a complete understanding of such a material at high temperatures has been slow. Attempts to apply the established principles of physical chemistry to the behavior of the individual components of this mixture have been beset by an almost complete lack of data on its chemical properties in the liquid state. This has necessitated the adoption of various methods of approximation based upon such assumptions as, for example, that for a given component the ratio of its mol fraction in the slag to that in the metal is a constant, or that the molecular composition of the liquid slag is the same as its crystalline constitution after solidification. From the thermodynamic viewpoint, such assumptions are merely useful dodges, which enable one to hazard a guess as to the magnitude of the more fundamental quantities, the chemical potentials and activities of the components of slag. The problem of determining the activity of each substance in an eight-component system seems too complex to be undertaken without the aid of generalizations derived from experimental data on similar systems containing a smaller number of components. Accordingly, it was planned in the present investigation to study the equilibrium of molten iron with the simplest

Jan 1, 1941

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By Dwight M. Lemmon

Encouraged by increased demand and higher prices for such metals as copper, lead, zinc, silver and tin, search was pressed in 1964 for mineral raw materials, especially in parts of the world that are relatively more stable politically and economically. New discoveries of metallic ores continued to be made, discoveries based on extensive geologic and geophysical work but nonetheless made in part because of good fortune.

Jan 2, 1965

By Edward Hyde

THE HIGH-TEMPERATURE SCALE IN OPTICAL PYROMETRY AT the basis of optical pyrometry lie the theoretical and experimental data of the so-called blackbody. The black body is essentially a theoretical conception, with certain simple properties attributed to it -fundamentally, the property that its radiation at any temperature is a unique function of the temperature and does not involve any other variables. As a theoretical conception, an equation has been developed by Boltzmann connecting the total radiant power with the temperature, and another equation by Planck connecting the distribution of radiant power throughout the spectrum with the temperature. The integral of the latter with respect to wave-length conduces to the former and permits the evaluation of the constant c1 of the Planck equation, ass given in the form. J-= cl?-5 c2 (1) e ? T ? 1 assuming that the constant Q of the Stefan-Boltzmann law E=a(T4-T40) is known. The other constant c2 is arrived at by other methods, which will be discussed later. This equation for the black body lies at the foundation of optical pyrometry. To make the discussion complete, it should be stated that the theoretical black body is quite closely realized by a hollow enclosure with walls at a uniform temperature and radiating through a small orifice. The electrically heated black body, first introduced by Lummer and Kurlbaum, is an essential part of the equipment of a pyrometric research or testing laboratory. Numerous investigations have shown that its radiation conforms to that of the theoretical black body within experimental errors. Hence by operating the electrically heated black body at the melting point of some pure metal for which the temperature of melting has been determined on the vas scale. a standard is obtained for comparison with

Jan 9, 1919

By Karl Fetters, John Chipman

The relationship between the composition of the slag and that of the underlying metal during the refining of a heat of liquid steel may best be studied in the light of the two broad physicochemical concepts of equilibrium and reaction rate. Actual steel-making processes, typified by basic open-hearth practice, involve such complexities of operating variables that it is impossible to distinguish with any degree of certainty between the general limiting conditions imposed by chemical equilibrium and the effects associated with rates of diffusion or of chemical reaction. Further advances in the physical chemistry of steelmaking will depend upon our ability to distinguish clearly between these two kinds of effects, and the experimental work that must be done falls naturally into two classifications. The first is the study of chemical equilibrium that cannot be carried out with assurance under operating conditions but must be done in the laboratory. The second is the -subject of rates of reaction and diffusion and the mechanism of the process as a whole, which can best be studied under operating conditions. The latter is not entirely independent of the former, since its interpretation often requires a knowledge of the equilibrium state. It is the purpose of this and of several papers that will follow to present the results of labora- tory investigations of equilibria involving liquid steel and slag. Open-hearth slag is a complex mixture containing at least eight major components and perhaps twice as many whose influence may be classified as probably minor. It is not surprising that progress toward a complete understanding of such a material at high temperatures has been slow. Attempts to apply the established principles of physical chemistry to the behavior of the individual components of this mixture have been beset by an almost complete lack of data on its chemical properties in the liquid state. This has necessitated the adoption of various methods of approximation based upon such assumptions as, for example, that for a given component the ratio of its mol fraction in the slag to that in the metal is a constant, or that the molecular composition of the liquid slag is the same as its crystalline constitution after solidification. From the thermo-dynamic viewpoint, such assumptions are merely useful dodges, which enable one to hazard a guess as to the magnitude of the more fundamental quantities, the chemical potentials and activities of the components of slag. The problem of determining the activity of each substance in an eight-component svstem seems too complex to be undertaken without the aid of generalizations derived from experimental data on similar systems containing a smaller number of components. Accordingly, it was planned in the present investigation to study the equilibrium of molten iron with the simplest

Jan 1, 1941

By Karl Fetters, John Chipman

The relationship between the composition of the slag and that of the underlying metal during the refining of a heat of liquid steel may best be studied in the light of the two broad physicochemical concepts of equilibrium and reaction rate. Actual steel-making processes, typified by basic open-hearth practice, involve such complexities of operating variables that it is impossible to distinguish with any degree of certainty between the general limiting conditions imposed by chemical equilibrium and the effects associated with rates of diffusion or of chemical reaction. Further advances in the physical chemistry of steelmaking will depend upon our ability to distinguish clearly between these two kinds of effects, and the experimental work that must be done falls naturally into two classifications. The first is the study of chemical equilibrium that cannot be carried out with assurance under operating conditions but must be done in the laboratory. The second is the -subject of rates of reaction and diffusion and the mechanism of the process as a whole, which can best be studied under operating conditions. The latter is not entirely independent of the former, since its interpretation often requires a knowledge of the equilibrium state. It is the purpose of this and of several papers that will follow to present the results of labora- tory investigations of equilibria involving liquid steel and slag. Open-hearth slag is a complex mixture containing at least eight major components and perhaps twice as many whose influence may be classified as probably minor. It is not surprising that progress toward a complete understanding of such a material at high temperatures has been slow. Attempts to apply the established principles of physical chemistry to the behavior of the individual components of this mixture have been beset by an almost complete lack of data on its chemical properties in the liquid state. This has necessitated the adoption of various methods of approximation based upon such assumptions as, for example, that for a given component the ratio of its mol fraction in the slag to that in the metal is a constant, or that the molecular composition of the liquid slag is the same as its crystalline constitution after solidification. From the thermo-dynamic viewpoint, such assumptions are merely useful dodges, which enable one to hazard a guess as to the magnitude of the more fundamental quantities, the chemical potentials and activities of the components of slag. The problem of determining the activity of each substance in an eight-component svstem seems too complex to be undertaken without the aid of generalizations derived from experimental data on similar systems containing a smaller number of components. Accordingly, it was planned in the present investigation to study the equilibrium of molten iron with the simplest

Jan 1, 1941

By J. L. Huitt

Some of the problems associated with the acid treatment of oil wells are related to the control of the composition of formation treating acid. One test usually made at the well site is the determination of the acid concentration. Heretofore, the concentration of the acid delivered to the well site usually has been interpreted from a hydrometer measurement of the specific gravity of the acid solution. Experience has shown that this indirect measurement of acid concentration can give erroneous results. More reliable results are, of course, obtainable by the titration method; however, this method is not easily adapted to well-site testing. To overcome these objections, a device was developed for use in the field which permits determination of the concentration of treating acid both quickly and accurately at the time of the acid treatment. Its purpose was three-fold, namely, to determine: (1) the concentration of the fresh treating acid, (2) the concentration of the spent acid returning from the well, and (3) the solubility of formation samples in treating acid. The device was designed to operate on the principle of the stoichiometric relation between the calcium carbonate—hydrochloric acid reaction and the carbon dioxide gas resulting from the reaction. By confining the carbon dioxide gas within a reaction cell of the type shown in Fig. 1, the pressure inside the cell is increased. Since the pressure is an indication of the quantity of carbon dioxide gas produced, it may be used to estimate the concentration of the acid, provided an excess of calcium carbonate is used. From information on the volume of the reaction cell, the volume of acid used, and the pressure and temperature of the gas after the completion of the reaction, the concentration of the treating acid may be computed. The reaction cell is essentially a pressure vessel equipped with a pressure gage, temperature indicator. pressure release valve, and a special sample holder. Plastic and metal construction makes the cell both rugged and acid-resistant. The sample holder is so designed that a sample of calcium carbonate (or sample of carbonate rock) can be dropped into the acid

Jan 1, 1956

By Vito J. Colangelo

The primary object of this study was to determine the effect of ferrite and its orientation upon the mechanical properties of a precipitation -hardening stainless steel with particular attention to the short-transverse properties. The investigation consisted of Jour major parts : the preliminary investigation of billet properties, the effect of forging reduction and ferrite content upon mechanical properties, the effect of notch orientation upon impact strength, and the relationship of heat composition to ferrite content. Low ductility and impact strength in the short transverse direction were found to he associated with the orientation and shape of- the ferrite plates. It was also determined that impact strength varied with notch orientation. The test values obtained with the notch perpendicular to the plane of the ferrite plate were lower than those obtained in the notch-parallel condition. The over-all investigation showed that high ferrite contents in general had a deleterious effect upon mechanical properties and that the ferrite content could he minimized by exercising rigorous control of the heat composition. A careful balance of elements, nitrogen in particular, must he maintained in order to reduce the formation of ferrite. THE precipitation-hardening stainless steels were developed to fulfill a need for high-strength corrosion-resistant alloys. In the annealed condition they are soft and ductile and possess many of the desirable characteristics of the austenitic stainless steels. In the hardened condition, the alloys exhibit the high strength and hardness of the martensitic stainless steels. The alloy under consideration in this investigation has a nominal composition as follows: C Mn Si Cr Ni Mo N 0.13 0.95 0.25 15.50 4.30 2.75 0.10 The hardening mechanism is identical to that of other hardenable steels in that it depends upon the transformation of austenite to martensite. This alloy because of its annealed structure and its ability to be hardened combines the desirable forming and corrosion properties of the austenitic grades with the high hardness and strength levels attainable with the hardenable grades. The reason for this apparent duplicity of proper- ties can be explained by considering a basic metallurgical difference between the hardenable stainless steels and those of the austenitic group. Both types are austenitic at 1800°F but, while the martensitic grades transform to martensite upon rapid cooling to room temperature, the austenitic grades remain austenitic even when cooled to temperatures below room temperature. The major difference then is in the degree of austenite stability. This stability can quantitatively be described by the Ms temperature. The Ms is defined as that temperature at which austenite begins to transform to martensite. The austenitic grades for example may be cooled to -300°F without producing significant quantities of martensite. The hardenable stainless steels on the other hand have an Ms temperature in the vicinity of 400" to 700°F. In cooling to room temperature, these alloys traverse the entire Ms-Mf range and show almost complete transformation to martensite. The semiaustenitic stainless steel, however, occupies an intermediate position with respect to its austenite stability. The analysis is so balanced that the Ills temperature lies at or slightly above room temperature. The resulting alloy retains much of its austenite at room temperature and yet responds to hardening heat treatments. Achieving this delicate balance of elements is therefore of great importance. Slight imbalances of the equivalent Cr-Ni ratios frequently result in the presence of 6 ferrite. It is the effects of this ferrit with which we are concerned, more specifically the effect of the quantity and ferrite orientation upon mechanical properties, particularly ductility. PROCEDURE A) Preliminary Investigation of Billet and Forging Properties. In order to determine the effect of ferrite on billet properties, billet stock from three heats with various ferrite contents was utilized. Tensile specimens were obtained in the transverse and longitudinal directions from this material and heat-treated as shown in Tables I and 11. Forgings were made from these same heats, the purpose being to determine what effect, if any, the ferrite might have upon the mechanical properties. These forgings were made in such a manner as to elongate the ferrite in the longitudinal and transverse directions. The method of forging was as follows. A section was cut from a 6-in.-sq billet of Heat A and flat-forged to 1-1/2 in. thick. Working was done from one direction only with no edging passes as shown

Jan 1, 1965

By H. Stuart, L. Zwell, N. Ridley

specimen that was subjected to 700°C for 250 hr is shown in Fig. 2(c). The precipitates in this foil appear round and exhibit only very faint strain contrast. From this evidence, along with that described above for the symmetry of the strain field, it may be concluded that this coherent precipitate is spherical, which is generally the favored shape for coherent precipitates when the lattice parameter mismatch is small.12 These observations are consistent with the assumption that this precipitate is the y' (Ni3Al, Ti) phase. y' is known to be spherical in the early stages of precipitation. It is fcc and is similar in composition to the matrix and thus would have contrast similar to that of the matrix as do these precipitates. Direct identification of the spherical precipitate did not prove possible because of its low volume fraction and small size. The results of this investigation suggest that the increases in yield strength and the decreases in elongation observed in 45-Fe 30-Ni 20-Cr alloys containing about 0.4 pct A1 and 0.4 pct Ti on prolonged aging at 550" to 700°C are very likely due to the presence of a coherent, spherical precipitate, thought to be y'. Mi-crohardness measurements indicated that the precipitation of semicoherent M23C6 resulted in some matrix hardening. However, this precipitation process occurs much more rapidly than the changes in mechanical properties at these temperatures. 1C. L. Clark, J. J. B. Rutherford, A. B. Wilder, and M. A. Cordovi: J. Eng. Power, 1962, vol. 84, p. 258. 2 F. A. Comprelli and U. E. Wolff: USAEC Report GEAP-4745, General Electric Company November, 1964. 3C. N. Spalaris: A Monograph, USAEC Report GEAP-4633, General Electric Company, July, 1964. THERE have been many X-ray investigations of the room temperature lattice parameters of austenite which has been retained in quenched steels of various carbon contents. The results of these investigations have been collected by Wrazej,1 Wever et al.,2 and by Roberts3 and are included in Fig. 1 due to Pearson.4 The dashed line in Fig. 1 was considered by Roberts3 to most reliably describe the variation with carbon content of the lattice parameter of retained austenite. This line is given by the equation: a (Å) = 3.555 + 0.044 wt % C and recent unpublished measurements by one of the authors (LZ) support this relationship. The object of this communication is to draw attention to a relationship which describes the variation of the room temperature lattice parameter of 'equilibrium' austenite with carbon content, and which is different from that for retained austenite. The relationship a(Å) = 3.573 + 0.033 wt % C has been obtained from lattice parameter measurements made on equilibrium Fe-C austenites at elevated temperatures, which have been extrapolated to room temperature. The room temperature lattice parameter of 3.555Å which the Roberts' relationship gives for pure y-Fe is no: in agreement with the value of 3.573Å obtained when the high temperature lattice parameter data of Basinski et aL.5 and of Goldschmidt6 is extrapolated to room temperature. A linear extrapolation was

Jan 1, 1970

By H. R. Froning, R. O. Leach

In wertability alteration flooding, a chemical agent is rnoved through a reservoir by the flood water to increase oil recovery by decreasing the degree of wetting of the rock by the oil. Substantial amounts of the chemical may be lost during movement through the reservoir. The extent of the loss, and therefore the economics of the process, depends in some cases on factors which are difficult to reproduce in the laboratory. Therefore, a short-duration, low-cost field test method is needed to permit evaluation of chemical requirements under actual field conditions. This paper describes a small scale rest conducted at a single well for measuring chemical requirements, thereby giving a more reliable evaluation of this important factor in the applicability and economics of the process. In the rest a small wafer slug containing the chemical agent and a nonadsorbed tracer is displaced into the reservoir by a known volume of wafer. The well is then placed on producrion. Chemical loss per barrel of pore volume contacted is calculated from [he fractional recoveries of the agent tested and the nonadsorbed tracer. The method has been used to determine within the actual reservoirs the chemical requirements for both a sandstone and a dolomite reservoir. Several chemical agents are potentially available for wettability alteration flooding, although none is universally applicable. For some applications of the method, chemical costs per barrel of additional oil recovered can be substantially less than one dollar. INTRODUCTION Wettability alteration flooding provides a means of increasing oil recovery from reservoirs by decreasing the degree of wetting of the rock by the oil and increasing the displacement efficiency of the flood water. Earlier studies demonstrated a relationship between oil recovery during waterflooding and the degree of wetting of a rock surface by an oil. The application of wettability alteration flooding to the Harrisburg field of Nebraska provided a field test' of this recovery process. Subsequently, additional laboratory and field tests have developed additional procedures for evaluating wettability alteration flooding, and have indicated where the process may be applicable. Applicability of this process to specific reservoirs is determined by a progression of tests to determine sus- ceptibility of the reservoir to alteration of its wettability, to indicate the degree of recovery improvement and to estimate the amount of chemical required to process the reservoir. The economics of applying improved oil recovery processes depends not only upon the degree of improvement in oil recovery achievable by the process but also upon the process costs and the timing of the income and the investment. Emphasis in this paper is on the expenditure aspects of the process. The work reported in this paper indicates that the chemical investments required for wettability alteration flooding are substantial. For evaluating the economics of a potential flooding application it is imperative that a sound estimate of the chemical requirements be made for the reservoir. Generally, true reservoir conditions are not adequately simulated in laboratory chemical propagation tests. Because of wide well spacings, many years might be required to obtain chemical propagation data from conventional pilots or inter-well tests. Consequently, n short-duration, low-cost method is needed to determine chemical requirements in the field. The potential applicability of wettability alteration flooding is discussed, as well as the economics of wettability alteration with respect to the inherent and imposed restrictions on the timing of income and investments. DETERMINATION OF CHEMICAL REQUIREMENTS In the process of moving a chemical bank through reservoir rock, some of the chemical agent lags too far behind the flood front to be effective or is otherwise lost to the reservoir system. The extent to which these losses occur overshadows the reductions in chemical concentration due to diffusion and to mixing with the reservoir fluids. Experience indicates that almost without exception, chemicals which induce a wetting change undergo either sorption reactions or chemical reactions with mineral constituents of the pore surfaces. Other reactions may occur between the added chemical and the reservoir oil and water. Even in limiting consideration to reactions of the relatively inexpensive inorganic salts, bases and acids, the reactions may be exceedingly complex. Reservoir pore surfaces consist of more than silica in sandstone reservoirs, and more than calcite or dolomite in carbonate reservoirs. Many mineral species are present, each exhibiting specific tendencies to react with an injected chemical. The reactions which occur can consume enough of the agent to have an important effect on economics. These reactions can cause a change in pH of the chemical bank, or may remove some of the active chemical by precipitation, adsorption or reaction to form a new chemical which may or may not be effective in

T.B.King (Depaytment of Metallurgy, Massachusetts Institute of Technology)— A valuable contribution of the authors is in the factual information which they have been able to gather; this type of information is quite difficult to obtain. In many respects, however, it would have been better if they had not subsequently embarked on a discussion of the chemistry of the converter process. It seems inconceivable that the authors do not refer to the papers of Schuhmann and his associates14 which have set the thermodynamic foundation for the whole copper smelting operation. In addition, a very useful review on the physical chemistry of copper smelting by Ruddle 5 appeared as long ago as 1953. An examination of this literature would have convinced the authors that there is no cause to be surprised at a correlation between the magnetic content and the silica content of converter slags, though they rightly point out that one should distinguish between the total magnetite content of the slag and the amount of magnetite which may be considered to be in solution. It is not true that the lowest melting converter slag is that corresponding to the eutectic between ferrous oxide and silica. The simplest slag system which can be considered is a three-component system, since both ferric and ferrous iron are present. As Schuhmann, Powell, and Michal have shown, there are lower melting compositions than this eutectic in the ternary system. The most unfortunate impression given by this paper is that the driving force for chemical reaction is determined by the heat of reaction: of course the entropy change must be taken into account. It would have been more correct to list, in Table VI, values for free energies of formation. Nor can it be said that the data in Table VI represent the "best available data." They do not corregtond with any of the recent, acknowledged sources. F. E. Lathe and L. Hodnett(author's reply)— We are pleased that Dr. King finds the factual information in our uawer of some interest. Dr. King suggests that it would have been better if our analysis and discussion of the data had been omitted, largely because our list of references is so. incomplete. If he will carefully read our introduction, he will see that the questionnaire was sent out in the hope of obtaining data which would throw light on certain questions relating to the use of converter refractories. We did not attempt (nor would the AIME have published!) a complete review of the literature on copper converting, as Dr. King has apparently assumed, nor indeed a complete analysis of the data submitted, but tried only to find a sound basis for the choice of refractories, taking into consideration common variations in converter practice. We hope our paper indicates that, by raising the silica content of the converter slag and operating at a higher temperature, the normal circulating load of magnetite can be greatly reduced, and the whole reverberatory-converter operation improved to a major degree, with resultant important savings. Under such operating conditions, chrome-magnesite brick may be expected to stand up better than those of straight magnesite. Regardless of the choice as between these brick types, however, we find the cost of converter refractories to be so low in comparison with other converter costs as to justify operation under the more severe conditions suggested. Valuable as are the papers by Schuhmann and associates and the book by Ruddle, we make no apology for omitting reference to them, nor for using heats of reaction without mention of entropy changes or free energies of formation. Our primary object was to interest the practicing copper metallurgist, with whose language we may claim to be fairly familiar; we think it would have been unwise to include the highly theoretical phases of the subject which Dr. King suggests. The interest shown in our preliminary paper presented at the New York meeting in 1956, and the trends in practice whtat we have observed since that time, suggest that we did not wholly miss the target. In conclusion, we sincerely hope that Professors King and Schuhmann will independently review the data obtained in our questionnaire and submit a paper giving their own recommendations as to the choice of refractories and the particular converter operating conditions which will result in the lowest overall cost of copper smelting and converting.

Jan 1, 1960

By Charles Luner

ALTHOUGH the kinetics of the atmospheric oxidation of tin have been studied,1-3 the kinetics in pure oxygen have not been reported. This note presents some results of the kinetics of the oxidation of tin foil in pure oxygen. The tin foil used in this investigation was 99.78 pct pure, the two major impurities being Pb (0.17 pct) and Sb (0.024 pct). The foil was degreased and air-dried prior to oxidation. The air-formed film was estimated by coulometric reduction4 of the surface oxides to be about 25A. The samples, which were in strip form and had a total geometric surface area of about 300 sq cm, were first evacuated at room temperature in an oxidation bulb to 1 X 10 -5 mm Hg and subsequently degassed for 1 hr at the temperature of the experiment. Spectroscopically pure oxygen was then introduced into the bulb. The rates of oxidation were measured by following the rate of pressure change due to oxygen consumption in a closed system, the volume of which was sufficiently large so that the pressure change during an experiment was 10 to 15 per cent of the total pressure. An oil-mercury manometer,5 with a sensitivity of 3 X x mm Hg (which corresponds approximately to 5 X 10 -7 gm of oxygen) was used to measure the pressure change. The oxidation bulb was heated by an oil-bath and controlled to within -10.3 C. The reproducibility of the rates was good, as determined by the coincidence of rates at 190oC for duplicate experiments. Fig. 1 shows the oxidation curves in the temperature range 168 to 211.5oC at 8 mm Hg pressure. The effect of pressure on the rate of oxidation at 190°C is also shown. The rate of oxidation was not markedly affected by changes in pressure in the range 4 to 9 mm Hg, except perhaps at the lowest pressure, 4 mm Hg, where after about 70 min there appeared to be a decline in the rate, as compared with the rate at the higher pressures. At the lower tem- perature, 168oC, and for short reaction times, it is difficult to distinguish between a linear relationship and a slight curvature in the oxidation rate. However, for longer times, there was a somewhat larger indication of curvature. The samples after oxidation were gold-colored in appearance. The oxide that was formed at 170°C was identified as a-SnO by reflection electron diffraction. This is in agreement with results obtained by other workers.6, 7 The rate data best fitted the logarithmic-oxidation rate law, w = K1n ln(1 + -t/to) [1] where w is the weight of oxygen consumed, t is the time, and K In, and to are constants. First estimates to were obtained according to the method of Taylor Thon8 and were then employed to obtain the best simuItaneous estimates of to and K In, that would fit the logarithmic expression. These estimates were found numerically, so that the residual variance could be minimized. The calculations were performed on an

Jan 1, 1961

By P. D. I. Honeyman

CHANGING trends in concentration, involving regrinding with the subsequent production of a finely divided, high-grade flotation product, presents a real problem to the modern copper smelter. In the treatment of such a material, handling difficulties are numerous and potential possible losses may be very great. In many plants, of course, preliminary roasting of the furnace charge remains an economical necessity. Under such circumstances, the operator has no alternative except to follow orthodox roaster reverberatory practice, though taking all possible precautions to avoid excessive dust losses and bad working conditions. In other plants, roasting is not only unnecessary but would be highly undesirable, and at best the charge would be merely dried before entering the reverberatory furnace. In the latter case the possibilities of raw charging loom large. The Miami plant of the International Smelting Co. handles the entire output of concentrates of the several mining companies operating in the Globe-Miami district. All of these companies produce a flotation concentrate which, at the Miami Copper Co. particularly, is all reground and is high in grade. In addition, the Inspiration Copper Co. ships a substantial tonnage of high-grade cement copper to the smelter from its leaching plant. Following the flow sheet of the original plant, all such material received was bedded, dried in Wedge furnaces and smelted in reverberatory furnaces. At times during the history of the plant it has been necessary to carry the drying operation further, to a partial roast, before reverberatory smelting. Since the charge contained over 80 per cent flotation concentrates, the handling of which in a dried condition was at best a dusty job, unusual precautions were taken to cut down dust losses. The Wedge furnace plant was equipped with a Cottrell treater and all hoppers and calcine cars were carefully designed to cut down dust loss in transferring the so-called calcine from hoppers to car and from car to furnace. In the furnace itself the dusting problem was a severe one. Arch erosion was very rapid and flues and waste-heat boilers rapidly filled up with a partly smelted flue dust.

Jan 1, 1932

By R. W. Vander Laan

Conneaut has a long and illustrious history as a major Great Lakes port for coal and iron ore. The first dock was built in 1892 for unloading iron ore from the Mesabi Range for shipment to the Pittsburgh steel mills via the Shenango & Lake Erie Railroad, later to become the Bessemer & Lake Erie Railroad. The Pittsburgh & Conneaut Dock Company was incorporated in 1893. The world's first Hulett automatic ore unloader was constructed at Conneaut in 1899. Steam operated, it was the model for the giant electric Huletts used today, named after its inventor, George Hulett, who was a Conneaut resident.

Jan 3, 1974

By P. D. I. Honeyman

Changing trends in concentration, involving regrinding with the subsequent production of a finely divided, high-grade flotation product, presents a real problem to the modern copper smelter. In the treatment of such a material, handling difficulties are numerous and potential possible losses may be very great. In many plants, of course, preliminary roasting of the furnace charge remains an economical necessity. Under such circumstances, the operator has no alternative except to follow orthodox roaster reverberatory practice, though taking all possible precautions to avoid excessive dust losses and bad working conditions. In other plants, roasting is not only unnecessary but would be highly undesirable, and at best the charge would be merely dried before entering the reverberatory furnace. In the latter case the possibilities of raw charging loom large. The Miami plant of the International Smelting Co. handles the entire output of concentrates of the several mining companies operating in the Globe-Miami district. All of these companies produce a flotation concentrate which, at the Miami Copper Co. particularly, is all reground and is high in grade. In addition, the Inspiration Copper Co. ships a substantial tonnage of high-grade cement copper to the smelter from its leaching plant. Following the flow sheet of the original plant, all such material received was bedded, dried in Wedge furnaces and smelted in reverberatory furnaces. At times during the history of the plant it has been necessary to carry the drying operation further, to a partial roast, before reverberatory smelting. Since the charge contained over 80 per cent flotation concentrates, the handling of which in a dried condition was at best a dusty job, unusual precautions were taken to cut down dust losses. The Wedge furnace plant was equipped with a Cottrell treater and all hoppers and calcine cars were carefully designed to cut down dust loss in transferring the so-called calcine from hoppers to car and from car to furnace. In the furnace itself the dusting problem was a severe one. Arch erosion was very rapid and flues and waste-heat boilers rapidly filled up with a partly smelted flue dust.

Jan 1, 1934

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach's work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,' who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750'F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968