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By P. E. Demmler

The apparatus in which the process of bright annealing of copper wire was carried out consisted of a section of iron pipe, 6 ft. long and 3 ft. in diameter. The pipe was provided with flanges to which were bolted the end plates for sealing, also with inlet and outlet tubes to allow for the displacement of the air in the pipe by natural gas. After charging with copper wire, sealing and displacing the air, the pipe was heated to 350' C. (662" F.). It was expected that the natural gas would furnish a neutral atmosphere which would prevent oxidation and give a satisfactory bright-annealed product. It was found, however, that the outer layers of wire were discolored and not suited for the use for which they were mtended. To obtain an idea of what was taking place in the annealing furnace, skeins of the hard-drawn wire were placed in a glass tube so that all changes in appearance could be observed as they were heated to different temperatures and under varying conditions. The temperature in each case was determined by means of a thermocouple placed in the tube close to the wire. Following is a summary of the results of these experiments: 1. When the wire was heated for 1 hr. in a current of natural gas at a temperature of 350") 400") or 500" C. (662", 752", or 932" F., respectively), there was a marked darkening of the wire throughout the skein. 2. When heated for 1 hr. in natural gas at a temperature of 600" C. (1112' F.), there was no coloration, the wire remaining clean and bright. 3. When heated in natural gas to 350" C. until darkened and the treatment continued with the temperature raised to 600' C., the coloration disappeared and the wire became clean and bright.

Jan 1, 1923

By P. E. Demmler

The apparatus in which the process of bright annealing of copper wire was carried out consisted of a section of iron pipe, 6 ft. long and 3 ft. in diameter. The pipe was provided with flanges to which were bolted the end plates for sealing, also with inlet and outlet tubes to allow for the displacement of the air in the pipe by natural gas. After charging with copper wire, sealing and displacing the air, the pipe was heated to 350' C. (662" F.). It was expected that the natural gas would furnish a neutral atmosphere which would prevent oxidation and give a satisfactory bright-annealed product. It was found, however, that the outer layers of wire were discolored and not suited for the use for which they were mtended. To obtain an idea of what was taking place in the annealing furnace, skeins of the hard-drawn wire were placed in a glass tube so that all changes in appearance could be observed as they were heated to different temperatures and under varying conditions. The temperature in each case was determined by means of a thermocouple placed in the tube close to the wire. Following is a summary of the results of these experiments: 1. When the wire was heated for 1 hr. in a current of natural gas at a temperature of 350") 400") or 500" C. (662", 752", or 932" F., respectively), there was a marked darkening of the wire throughout the skein. 2. When heated for 1 hr. in natural gas at a temperature of 600" C. (1112' F.), there was no coloration, the wire remaining clean and bright. 3. When heated in natural gas to 350" C. until darkened and the treatment continued with the temperature raised to 600' C., the coloration disappeared and the wire became clean and bright.

Jan 1, 1923

By F. von Gemmingen, E. J. Fasiska, L. Zwell

EARLIER studies of the dependence of creep on structure1 and of the dependence of creep rupture on creep behavior2 did not include detailed discussion of the phases present in the specimens under examination. It is of interest to determine the nature and amounts of such phases present since it is well known that these are dependent on composition, heat treatment and creep conditions.3 This investigation has therefore been undertaken to identify these constituents and to determine their relative amounts. This report presents the results of this investigation and describes an improved "extraction replica" technique developed in the course of the work. The composition of the Type 316 austenitic stainless steels studied in this investigation is given in Table I. The specimens were solution treated at 2000°F for 1/2 hr and water quenched. Those specimens subjected to prestrain at room temperature Methods for extracting precipitate particles from materials for electron and X-ray diffraction analysis have been described by Fisher,4 Smith and Nutting: and Booker and coworkers.6'7 Electrolytic extraction methods have been described by Andrews and Hughes.8 The first two methods have been used at this Laboratory, but have not proved satisfactory for many problems requiring X-ray diffraction analysis. It has been difficult to remove the replicas or to avoid tearing them during removal. These difficulties are overcome by backing the replica with a water-soluble plastic such as Dupont 51-05 Elvanol (polyvinyl alcohol). The backing increases the thickness of the replica so that it can be mechanically stripped from unloosened particles without folding or tearing. This procedure eliminates the stripping of wet replicas, which usually have a low tear strength. By stripping replicas after drying, it is possible to extract partially loosened particles which otherwise would remain imbedded in the metal. The modified method is as follows: after the specimen is polished, it is etched for 60 min in modified glyceregia consisting of 30 ml glycerol, 7 ml nitric acid, and 4 ml of hydrochloric acid. The sample is then washed, air dried, and coated with a 20 pct Baker and Adamson 1611 collodion (85 pct amyl acetate by volume) film. After the collodion film is dry (about 15 min), the sample is again etched in the modified glyceregia for 50 min, washed with isopropyl alcohol (to prevent dissolving the collodion) and air dried. A very thick coat of polyvinyl alcohol (about 50 pct solution "Elvanol Dupont 51-05" in water) is poured over the sample and is permitted to dry for about 24 hr. The composite film containing the precipitates is then stripped from the specimen and floated, polyvinyl alcohol side down, in water (at about 50°C) until the polyvinyl alcohol dissolves. This usually takes about 15 min. Should any of the polyvinyl alcohol remain on the replica, it does not give a crystalline diffraction pattern and therefore does not hinder identification of the precipitates. The extraction replica, floating in water, is picked up on a glass fiber and mounted in the Debye-Scherrer camera for X-ray diffraction analysis. Concentration of the etchant, and also etching time, had to be increased for several of the samples. Fig. 1 shows two extraction replicas taken from different areas of spec. M74-37; X-ray analysis showed a strong diffraction pattern of M23C6 and a medium one of u phase. A

Jan 1, 1962

By Albert S. Trube

Increasing emphasis is being placed on the necessity for obtaining reasonably accurate estimates of the physical properties of reservoir fluids well in advance of more accurate laboratory data. One such factor is the isothermal coefficient of expansion of an undersaturated hydrocarbon liquid which may be contained in a particular reservoir. This coefficient, or liquid "compressibility", has often been assumed to be relatively insensitive and nearly constant. Although this assumption may be nearly correct in the case of high specific gravity liquids, it cannot apply in the case of medium to low specific gravity liquids. Any treatment of the nature of liquid compressibilities must give consideration to the variable nature of the isothermal expansion coefficient and the fact that it can be both pressure sensitive and temperature sensitive. The isothermal coefficient of expansion, or compressibility, of a substance is defined as -c = 1/V (?V/?p)T......(1) The value of Eq. 1 may be approximated for a finite pressure change by using the well-known relation, c = V1 - V1/Ve (p2-p1), ........(2) in which p1 > p1 and V2 > V2 and V1 + V2/2. The instantaneous compressibility may also be estimated from the slope of a curve on which log V is plotted vs pa. In this instance, it has been shown that c = In V1/V2/p2-p1 ...........(3) Eq. 3 may be used for variable compressibilities by plot-ting V vs p on semi-log paper. In this case, the instan-taneous or point compressibility is c = 2.303 m.......... . (4) in which m is the slope of the curve at a point in log cycles per psi. ISOTHERMAL COMPRESSIBILITY OF UNDERSATURATED LIQUID In the case of gases, the compressibility has been defined by Muskat' and others as Co = 1/p - ?z/z?p ..........(5) This was later generalized through application of the theorem of corresponding states' to co = 1/pr - (?z/z?pr) T8 ........(6) in which c, is defined as the pseudo-reduced compres-sibility and is numerically equal to (c.p,) and the sign is arbitrarily changed for mathematical convenience. Eq. 6 is general and applies to gases and liquids. In the case of liquids, c. = c1,pe, but if Eq. 6 is used, values of z and ?z/?p, must be determined for the liquid in question. The difficulty of obtaining accurate values of ?z/?p,, particularly in the region where T, is approaching 1.00, was pointed out in the previous paper'. This method of approach is unreliable for extension into computations of liquid compressibilities. On the other hand, c, can also be defined as follows: - Cr = 1/Vr (?Vr/?pr) Tr ......(7) and from which, Cr = 1/pr (?pr/?pr) Tr .....(8) In accordance with the theorem of corresponding states, Vr = V/Vr, p, = p/pr and pr = p/pr. Ref. 2 pro-vides an excellent source of reduced density, reduced pressure and reduced temperature data for a wide variety of fluids. For the purpose of this investigation, the set of fluids2 having ze = 0.27 was chosen because it in-cludes most of the heavier hydrocarbons usually found in those complex mixtures loosely defined as "reservoir oils". Data on undersaturated liquids in Ref. 2 were rearranged to conform with Eq. 8. To simplify the computation of cr, the isothermal p, data were plotted vs the log of pr, in which case for any straight line or tangent cr = 1/M pr pr .....(9)

Jan 1, 1958

By M. E. Volin, D. W. Fuerstenau, A. L. Mular

This paper presents the results of an investigation of the effect of feed size on the integral rate at which feed material is dry ground in a laboratory rod mill. The data are interpreted in terms of the Gaudin-Meloy distribution equation. The equation, Mo — Mt/t = Aoxo r-1, is found to hold for feed sizes smaller than some critical size or for grinding times larger than some critical time. It is shown that a feed grindability is related to this critical size, which appears to be the transition between predominately impact and predominately attrition grinding. Detailed research on feed size effects in comminution has been rather limited. Gaudin1 ground single-sieve fractions of quartz for extended time periods (four hours) in a laboratory ball mill. His work, which was designed to study the nature of size distributions, showed that there is a critical feed size above which comminution occurs primarily by attrition. For his system, the critical size was about 2-mm when using 22-mm balls. In a more recent investigation2 single-sieve fractions of quartz were ground in a laboratory rod mill for constant time periods (15 min) to determine how feed size affects the grindability of the material. This work showed that grindability is essentially independent of feed size in the rod mill after this moderately long grinding period. To further clarify this observation, a study in which feed size and grinding times are varied over a fairly wide range, and particularly, a study of the dependence of the integral rate of grinding on feed size during the initial stages of rod milling is necessary. For an analysis of such data, it is desirable to use a parameter which is very sensitive to change during the initial grinding period when reduction ratios are

Jan 1, 1964

By Janshi Sen

Vertical-intensity magnetometers, for instance the Hotchkiss Superdip and the Askania vertical field balance, are now widely used, because vertical-intensity charts give definite information for the location of upper pole, dip and strike, and approximate shape of the deposit. Again, a slow and steady increase of dip over a large area indicates a large deep-lying deposit, while a large dip limited to a small area and falling away rapidly suggests a small and shallow one. The complication comes more from the richness of the ore. A large body of lean ore near the surface might produce the same vertical-intensity chart as a rich ore at depth. This paper presents a method for calculating the maximum depth of a single-pole deposit and another for a two-pole mineral body, by utilizing data of both vertical and horizontal intensities as obtained by a Thalen-Tiberg magnetometer. As shown on the left side of Fig. I, lean ore, rich ore and a single pole produce the same magnetic field. The depth of the pole, where G is the vertical intensity at point A due to the pole; F, the horizontal intensity of the same; and a, the distance from the point of maximum vertical intensity or the vertical projection of the pole on the surface to the point of observation A. If an entirely covered deposit is indicated by magnetic measurements and boring cost estimated from the calculated depth is so reasonable as to encourage drilling, the ore should be struck somewhere within the limit of the calculated depth by the borehole. A number of such points as A should be taken for calculation, erratic results should be rejected and the average figure used for cost estimation.

Jan 1, 1946

By Janshi Sen

Vertical-intensity magnetometers, for instance the Hotchkiss Superdip and the Askania vertical field balance, are now widely used, because vertical-intensity charts give definite information for the location of upper pole, dip and strike, and approximate shape of the deposit. Again, a slow and steady increase of dip over a large area indicates a large deep-lying deposit, while a large dip limited to a small area and falling away rapidly suggests a small and shallow one. The complication comes more from the richness of the ore. A large body of lean ore near the surface might produce the same vertical-intensity chart as a rich ore at depth. This paper presents a method for calculating the maximum depth of a single-pole deposit and another for a two-pole mineral body, by utilizing data of both vertical and horizontal intensities as obtained by a Thalen-Tiberg magnetometer. As shown on the left side of Fig. I, lean ore, rich ore and a single pole produce the same magnetic field. The depth of the pole, where G is the vertical intensity at point A due to the pole; F, the horizontal intensity of the same; and a, the distance from the point of maximum vertical intensity or the vertical projection of the pole on the surface to the point of observation A. If an entirely covered deposit is indicated by magnetic measurements and boring cost estimated from the calculated depth is so reasonable as to encourage drilling, the ore should be struck somewhere within the limit of the calculated depth by the borehole. A number of such points as A should be taken for calculation, erratic results should be rejected and the average figure used for cost estimation.

Jan 1, 1946

By C. F. Quest, T. S. Washburn

The steel industry has a definite need in its tonnage mills for a formula relating expected tensile strength to the analysis of the steel. The McWilliam-Barnes1 and other less comprehensive formulas are used for this purpose, but these formulas were designed for an analysis range that does not include the medium manganese and silicon-bearing steels. This type of steel is being produced to meet the demand for tensile strength slightly higher than that of ordinary structural steel but not high enough to justify expensive alloy steels. The purpose of this paper is to present a somewhat more comprehensive formula based on data accumulated over a number of years by the Inland Steel Co., and to discuss the method followed in obtaining a formula to fit the data. The resultant formula admittedly is still weak in some respects, but for the expanded analysis range appears to be an improvement over the other formulas. It is hoped that with the collection of more data and possible collaboration with other mills studying this problem it will be possible to work out a more nearly perfect formula. Several publications have been issued on this subject. In some, the equation type of relation was evolved while others made a combination of tables and an equation. The latter include work by Campbel12,3 and Webster.4,5 Campbell classified the steels as acid and basic and applied a different formula to each. For basic steels, he used the equation: Teosile etrength = 41500 + 770C + 1000P + yMn [1 y was a variable depending on the carbon and manganese content of the steel and was listed in tables. Webster investigated acid Bessemer steel and developed the equation: Tensile strength = 38000 + 800C + xTP+ yMn [2]

Jan 1, 1940

By C. F. Quest, T. S. Washburn

The steel industry has a definite need in its tonnage mills for a formula relating expected tensile strength to the analysis of the steel. The McWilliam-Barnes1 and other less comprehensive formulas are used for this purpose, but these formulas were designed for an analysis range that does not include the medium manganese and silicon-bearing steels. This type of steel is being produced to meet the demand for tensile strength slightly higher than that of ordinary structural steel but not high enough to justify expensive alloy steels. The purpose of this paper is to present a somewhat more comprehensive formula based on data accumulated over a number of years by the Inland Steel Co., and to discuss the method followed in obtaining a formula to fit the data. The resultant formula admittedly is still weak in some respects, but for the expanded analysis range appears to be an improvement over the other formulas. It is hoped that with the collection of more data and possible collaboration with other mills studying this problem it will be possible to work out a more nearly perfect formula. Several publications have been issued on this subject. In some, the equation type of relation was evolved while others made a combination of tables and an equation. The latter include work by Campbel12,3 and Webster.4,5 Campbell classified the steels as acid and basic and applied a different formula to each. For basic steels, he used the equation: Teosile etrength = 41500 + 770C + 1000P + yMn [1 y was a variable depending on the carbon and manganese content of the steel and was listed in tables. Webster investigated acid Bessemer steel and developed the equation: Tensile strength = 38000 + 800C + xTP+ yMn [2]

Jan 1, 1940

By C. F. Quest

THE steel industry has a definite need in its tonnage mills for a formula relating expected tensile strength to the analysis of the steel. The McWilliam-Barnes1 and other less comprehensive formulas are used for this purpose, but these formulas were designed for an analysis range that does not include the medium manganese and silicon-bearing steels. This type of steel is being produced to meet the demand for tensile strength slightly higher than that of ordinary structural steel but not high enough to justify expensive alloy steels. The purpose of this paper is to present a somewhat more compre-hensive formula based on data accumulated over a number of years by the Inland Steel Co., and to discuss the method followed in obtaining a formula to fit the data. The resultant formula admittedly is still weak in some respects, but for the expanded analysis range appears to be an improvement over the other formulas. It is hoped that with the collec-tion of more data and possible collaboration with other mills studying this problem it will be possible to work out a more nearly perfect formula. Several publications have been issued on this subject. In some, the equation type of relation was evolved while others made a combina-tion of tables and an equation. The latter include work by Campbell2,3 and Webster.4,5 Campbell classified the steels as acid and basic and applied a different formula to each. For basic steels, he used the equation: Tensile strength = 41500 + 770C + 1000P + yMn [1] y was a variable depending on the carbon and manganese content of the steel and was listed in tables, Webster investigated acid Bessemer steel and developed the equation Tensile strength = 38000 + 800C + xP + yMn [2]

Jan 1, 1940

In March 1956 a conference on geochemical methods of prospecting for ore deposits was held in Moscow. This conference was the culmination of a ten-year period of extremely rapid increase in both research and routine application of geochemical prospecting methods in the USSR. This activity was divided among groups centered in extremely widely separated bases of operation, ranging from Moscow and Leningrad in the West, Yerevan in the Caucasus, and Alma-Ata in Central Asia to Chita near the Manchurian frontier in the Far-East. The All-Union Conference on Geochemical Methods of Prospecting for Ore Deposits, as the meeting was called, was the first opportunity for these scientists from many parts of the country to meet and exchange experiences. It also served to introduce members of the different research laboratories located in the city of Moscow itself, where adequate channels of technical communication had not yet been established. As a result of the Conference, it was resolved that a concerted effort should be made for the participants to publish the results of their work. Two books have appeared as a direct response to this resolution. I. I. Ginzburg prepared a synthesis of the field of geochemical prospecting for minerals based on the material presented at the Conference. This volume has been translated into English and is now available. In addition, the individual papers presented at the Conference were assembled into a symposium volume and published in 1957 under the editorship of V. I. Krasnikov. Unless otherwise noted, these two books have supplied the source material for the present appraisal of the status of geochemical prospecting in the USSR. It is thus about four to five years old. In the years following the conference, the literature has carried a substantial volume of technical papers, together with a few monographs pertaining to specialized aspects of geochemical prospecting.

Jan 6, 1960

By Z. F. Oszter, D. Vincent, W. K. Behrands

With the expansion of open pit operations, belt conveyors are going to be used in the 13 608 to 18 144 t/h (15,000 to 20,000 stph) capacity range, which calls for a review of some of the horsepower calculation methods. This paper presents methods (based on German research data, field tests and theoretical considerations) for the evaluation of the Ky factor in the CEMA formula for belt conveyors of large carrying capacity, which fall beyond the limits of the data given in tables in the CEMA book. (The CEMA limits are 407 N\\m (300 lb ft) and Tave = 7.3 Mg (16,000 lb). At these large loads, the impression resistance of the belting on the idlers plays a major role, which in turn influences the magnitude of the drive horse power required. An example will illustrate the order of magnitude difference of the horsepower values obtained by using a conventional calculation method and the suggested method, as well as the beneficcia1 influence of the 4-roll idler in comparison to the standard 3-roll unit for a large caving capacity belt conveyor. This paper concerns itself with the analysis of the resistance to motion of belt conveyors, emphasizing the evaluation of the frictional resistance to motion due to load and belt pressure on the idlers and the flexing resistance of the belt and material when passing over the idlers. In the case of long and heavily loaded belt conveyors, the aforementioned resistances reach extremely high values calling for close analysis of the phenomena, presently not calculable with normally used formulas. This paper establishes correlation between experimental and empirical data presenting practical formulas a tool for the designer of high-capacity belt conveyors. The application of the formula is illustrated in an example in the Appendix.

Jan 1, 1981

By Ralph W. Bailey, William B. Price

During the past three or four years, the fabricators of silicon-bronze alloys have endeavored to induce users of phosphor bronze to use instead the silicon-bronze alloys, claiming that the silicon bronzes are superior to the phosphor bronzes for switches and springs, or where high fatigue resistance is desired. This paper gives the results of tests comparing several phosphor bronzes with a 3 per cent silicon bronze and a copper-nickel-tin alloy (Adnic), all processed by the Scovill Manufacturing Co. So far as the authors are aware, sheet-metal fatigue tests have not been made on any of the alloys included in this report, except on one phosphor bronze, material C, Table 1, which was tested by Townsend and Greenall1. Endurance Limit The majority of fatigue tests are designed to determine the endurance limit of a material. The number of repetitions of stress that will serve to establish an endurance limit varies with different materials. For ferrous materials, H. F. Moore2 has shown that stresses that do not cause failure up to 10,000,000 stress cycles will not cause failure up to 100,000,000 (and sometimes to 1,000,000,000) cycles. Thus an endurance limit for ferrous materials can be determined with a minimum of 10,000,000 stress cycles. For nonferrous materials, no such generalization holds. R. R. Moore3 has shown that for manganese bronze and elektron metal, 13,000,000 and 28,000,000 cycles, respectively, will serve to determine an endurance limit, while certain duralumin specimens gave no indications of having reached an endurance limit up to 400,000,000 stress cycles. J. B. Johnson6 showed that an endurance limit for duralumin was not found by tests running up to 500,000,000 cycles. H. F. Moore2

Jan 1, 1937

By Boyd Dudley

The material presented in this paper is an abstract of a thesis submitted by the writer to the faculty of the Massachusetts Institute of Technology, as part requirement for the degree of Master of Science. The investigation was undertaken at the suggestion of Prof. H. 0. Hofman, and it was conducted, under his direction, in the laboratories of the Mining Department of the Institute. The purpose of the work was, first, to study some of the reactions that have been considered as a part of the mechanism of the chloridiz-ing roast, and second, to study the conditions under which nickel oxide and copper oxide may be chloridized. While the production of chlorine gas by various reactions during the chloridizing roast may not be primarily useful in the chloridation of metal oxides and compounds, it nevertheless serves a useful purpose in preventing the dissociation and decomposition of chlorides once they have been formed; for example, the dissociation of cupric chloride into cuprous chloride and chlorine. Therefore it was thought that a study of some chlorine-producing reactions would prove of interest, and the first series of experiments dealt with this phase of the subject. he object of the latter part of the work was to show the possibility of treating heavy sulphide ores, such as those of Sudbury, Ontario, containing much iron and small amounts of copper and nickel, by chloridizing and removing the copper, leaving an iron-nickel oxide product suitable for smelting in the blast furnace for nickel-bearing pig iron. The chloridizing of the copper would, of course, be preceded by a roast for the removal of sulphur, the sulphur oxides being available for the manufacture of sulphuric acid, if under the local conditions this product would be of commercial value. Reactions of the Chloridizing Roast Reaction of Sodium Chloride, Sulphur Trioxide, and Oxygen.—The first reaction studied was that involving the production of chlorine

Jan 1, 1915

By J. H. O’Dette

BLISTER formation on wrought aluminum products has been a matter of concern to aluminum fabricators for many years. The fact that blisters make their appearance during the final stages of fabrication means that much time and effort have been expended before it is evident that the material must be scrapped. This and the loss of production are ample reasons for embarking on a research program to find out more about blistering and possible methods of control. Many excellent papers on this subject have appeared in the technical literature in the last few years. In one of the more recent papers, Kostronl gives a fairly complete review of the problem of gas in aluminum and blistering in general. From the work of the various investigators, a general mechanism for the formation of blisters has evolved and may be summarized briefly as follows: Hydrogen gas is usually present in the cast ingot, in the atomic or ionic state, in excess of the solid solubility. At room temperature the gas atoms are relatively immobile, but at elevated temperatures they become mobile and diffuse to free surfaces where they associate to form molecules. If these free surfaces are discontinuities within the ingot then the associated gas molecules collect and build up considerable pressure until equilibrium is reached with the dissolved gas around the discontinuity. Since the solubility of the gas is proportional to the square root of the partial pressure it is evident that large pressures may be built up at the discontinuities. When the metal is rolled to sheet the pressure of the gas in these, discontinuities is sufficient to deform the surface of the sheet and form a blister, particularly when the strength of the material is reduced during the annealing. Although the mechanism of the formation of blisters was fairly well known, the actual impor- tance of the individual roles played by the gas and the discontinuities was not so well established that positive methods for control of blistering were at hand. It was the object of the investigation to learn more about the nature of the discontinuities giving rise to blistering and to develop methods of control. The investigation was carried out in three stages as follows: a) A study of the more commonly used methods of removing hydrogen from aluminum, such as fluxing and holding, and their effects on blistering. b) Location of the discontinuities giving rise to blistering. c) A study, by indirect methods, of the movement of gas in the metal and its effect on blistering, and the development of methods of blister control during fabrication. Removing Gas and Reducing Blistering by Fluxing or Holding-—The work of removing gas and reducing blistering by fluxing or holding was carried out on metal of Alcan 2s (1100) composition with an artificially high gas content. The high gas content was obtained by introducing water into the melt prior to casting; the water reacted with the aluminum forming A12O3 and hydrogen. The procedure was to raise the gas content by introducing water into an aluminum melt and using half the melt to cast one ingot immediately. The remaining metal was treated again with water to make up for the reduction in gas content during holding, while the first ingot was being cast, and then given a fluxing or holding treatment and cast into an ingot. Samples for gas determination were cast from the molten metal before and after the gassing operation; before, after, and during fluxing, and while casting. Samples were also cut from sections of the ingots. Gas determinations were made on these samples using the well known vacuum fusion technique. All ingots were hot rolled at 500°C to 0.250-in. slab which, in turn, was cold rolled to 0.040 in. sheet. The sheet was coiled and annealed for 2 hr at 500 °C and then cut into 5-in. squares which were inspected for

Jan 1, 1958

By M. P. Tixier, M. Gondouin, G. L. Simard

In the quantitative interpretation of the SP logs, the electrochemical component is generally taken equal to — K log Rm /Rw where K has the theoretical value corresponding to solutions of pure sodium chloride. This method may be misleading when relatively large quantities of salts other than NaCl are present in form-rrtion waters—as is generally the case for low salinities —or in gyp-base muds. In such cases recourse is made in the field to changing the K value or to adding a correction term to the equation on the basis of local experience. An investigation has been made in the laboratory of the influence of HCO3, SO4=, Ca++, and Mg++ on the amplitude of the SP deflection, which included in par-ricular determinations of the activity coefficients of Ca++ and Mg++. The theory, the experimental techniques and a tentative method for applying the results are described. So far, applications to actual field cases where chemical analyses of waters were available have provided an excellent confirmation of the proposed method. The case of the SP in very salty brines is also considered and it is shown that the use of activity data for sodium gives satisfactory results. HISTORICAL In early times of electrical logging, the SP curve was used exclusively as a tool for the location of permeable beds and the definition of their boundaries. Later, with the introduction of methods of quantitative analysis, attention was called to the possibility of deriving from the SP log some information on the formation water resistivity, which constitutes one essential element for the computation of water saturation from log data. The first laboratory experiments' in 1932 had shown that, as a result of electrochemical phenomena arising at the contact of the niud and the formation, the amplitude of the deflection of the SP curve was, at least partly, a function of the salt concentration of interstitial water and accordingly of its resistivity. It was indicated that the amplitude of the electrochemical component of the SP should be equal to K log R1/R2, R1 and R2 being the resistivities of the mud and of the formation water respectively. However, the exact value of the K coefficient was not determined at that time because the surface clay used for a laboratory model was far from an ideal shale membrane. Consequently, the way was not yet open towards quantitative interpretation. In the early forties, Tixier reported2, on the basis of field log observations, the following equation for the case of NaCl solutions, SP = -71 log f1c1/f2c2, c1 and c2 being the concentrations and f1, f2 the mean activity coefficients. The local variations observed in the empirical values of K, chiefly in the Rocky Mountains, led him to advance the opinion that, besides the relative amounts, the nature of the salts present in the solutions had a bearing on the magnitude of the SP. At about the same time Mounce and Rust- ad published laboratory results which emphasized the part played by the shale in the generation of the SP. On the basis of laboratory tests and theoretical considerations, Wyllie in 1948' published the following equation of the electrochemical SP for the case of NaCl solutions, SP= - 71 log (a1)m/(a2)m

Jan 1, 1958

By W. L. Kerlie, J. H. Richards

The variation in hydrogen content of basic open-hearth steels during refining and the effect of changing from steam to air atomization were studied. The water content of the furnace atmosphere, the slag basicity, and the degree of oxidation of the slag-metal system largely control the hydrogen in the steel. SMALL amounts of hydrogen have an adverse effect on the ductility of steel and a wide range of hydrogen contents has an adverse effect on the internal soundness of both ferrous and nonferrous castings. This has been of major concern to the metal industry, both manufacturers and fabricators, for many years. As one of the results of continuing investigations of the hydrogen problem, much has been learned about methods of reducing the hydrogen content of liquid metals below the relatively high levels that are normally associated with such phenomena as rising ingots and excessive porosity in sand casting. However, it was not until a reliable and simple method for sampling and analyzing liquid metal was developed that much progress was possible in quantitatively evaluating the effect of steelmaking practice on hydrogen contents at levels below 6 to 8 ppm. Throughout all the work described in the following presentation the Geffner pintube technique was used to obtain samples of liquid metal1 * and the tin-fusion method, developed at Massachusetts Institute of Technology,2 was used to analyze the samples. Before attempting a systematic experimental program for minimizing the hydrogen content of open-hearth steels, it was necessary to determine the variation in hydrogen in the open-hearth bath during the normal processing of a heat. The logs of ten heats are illustrated in Figs. 1 through 7. The number at each point on the graphs refers to the number of pintube samples analyzed for hydrogen. An increase in the hydrogen content of the liquid metal during the early period of refining is apparent in all heats. There is evidence of a decrease in hydrogen later in the refining period, see Fig. 2, for example. Therefore, the existence of a maximum hydrogen content at some intermediate time during the refining period is anticipated. To test for the existence of a maximum, the data illustrated in Figs. 1 to 5 were grouped together so that they could be examined on a collectively comparable basis. The grouping was effected, as illustrated in Fig. 8, by superimposing Figs. 1 to 5 so that the apparent hydrogen maxima coincided at a fixed position, indicated by the zero on the time axis. Also, by vertical adjustment until the graphs appeared to the eye to be superimposed, the hydrogen scale was made to show the change in hydrogen content. That is, a standard amount was subtracted from the hydrogen values for each heat. Therefore, Fig. 8 represents a generalized presentation of the data and, for this reason, cannot be used to predict the actual hydrogen content of the bath during refining, but rather to show the probable rate of change in hydrogen during refining. Statistical examination of the grouped data in Fi.g. 8 shows that the apparent. increase and suhsequent decrease in hydrogen are real and confirms the existence of a maximum in general. The average increase In hydrogen during the early period of refining is between 0.8 and 1.3 ppm per hr, and the

Jan 1, 1958

By C. L. Sollenberger, Will Mitchell, Ford F. Miskell

Heat treatment of ore prior to comminution reduces power requirements for grinding, reduces grinding media wear, and improves recovery of iron values from a typical Minnesota magnetic taconite. Test data demonstrating this, as well as an analysis of the economics of commercial application of the technique, are presented. THE taconites in general are hard, tough ores, difficult to grind. Liberation of iron mineral constituents usually is accomplished by grinding the ore through at least 100 mesh, and often it has been found necessary to grind substantially through 325 mesh to achieve satisfactory recovery and grade in the concentration process. Because of the fineness of grind required and the enormous tonnages of material contemplated for treatment in the future, costs resulting from grinding media wear and power consumption, together with capital investment required for comminution, approach astronomical figures. Economy in any one of these elements per ton of material ground could very well reflect a considerable saving to the ferrous industry in yearly costs. With this in mind, the Research Laboratories of Allis-Chalmers Manufacturing Co. have launched a program to discover means of effecting this economy. The initial phase of the work as described here deals with a heat treatment of crushed raw ore, followed by thermal shock in cooling, for the preparation of rod mill feed. Several investigators1-" ave noted an improvement in the grindabilities of ores treated in this manner. One investigator2 subjected low grade iron ores to heat treatment in an electric furnace. Basing his conclusions on screen analyses of crushed products, he observed that treated ore was more easily crushed than the untreated. He reported that observation of the treated and untreated ore through a microscope revealed cracks following the grain boundaries in treated ore, whereas no cracks were present in untreated ore. However, few if any have quantified the improvement in terms of total hp hours saved, reduction of wear of grinding media, or reduction of capital costs of grinding equipment involved. By means of Bond rod mill and ball mill grindabilitiesh nd by comparative wear tests, the conditions maintained during this investigation have been definitely evaluated. Heat treatment experiments have been made on a batch scale in a muffle furnace, followed by continuous scale experiments in a rotary kiln under various conditions of temperature, atmosphere, retention time, and quenching to determine the combination that would give the greatest improvement in the grindability of a taconite without affecting adversely the magnetic susceptibility of the magnetite. From these data, relative costs have been calculated for grinding both untreated and heat- treated ore on a basis of plant capacity of 120 tons per hour. Heat requirements for a rotary kiln, as well as the kiln capacity required for the treatment, have been estimated. For these tests 50 tons of ore were obtained from the Aurora mine of the Erie Mining Co., Hibbing, Minn. The ore was reported7 to have been selected from the magnetic portion of the lower chert horizons. An average chemical analysis of' this portion is shown in Table I and an approximate mineralogi-cal analysis is shown in Table 11. No attempt was made to differentiate between the various silicates because the compositions vary widely on the different horizons and depend on the degree of oxidation. Minnesotite, however, is the predominant silicate. The siderite grains were dispersed throughout the ore but were essentially associated with the rock-forming minerals. In a series of preliminary tests in which batches of —6 mesh ore were heat-treated in a muffle fur-

Jan 1, 1953

By Will Mitchell, Ford F. Miskell, C. L. Sollenberger

Heat treatment of ore prior to comminution reduces power requirements for grinding, reduces grinding media wear, and improves recovery of iron values from a typical Minnesota magnetic taconite. Test data demonstrating this, as well as an analysis of the economics of commercial application of the technique, are presented. THE taconites in general are hard, tough ores, difficult to grind. Liberation of iron mineral constituents usually is accomplished by grinding the ore through at least 100 mesh, and often it has been found necessary to grind substantially through 325 mesh to achieve satisfactory recovery and grade in the concentration process. Because of the fineness of grind required and the enormous tonnages of material contemplated for treatment in the future, costs resulting from grinding media wear and power consumption, together with capital investment required for comminution, approach astronomical figures. Economy in any one of these elements per ton of material ground could very well reflect a considerable saving to the ferrous industry in yearly costs. With this in mind, the Research Laboratories of Allis-Chalmers Manufacturing Co. have launched a program to discover means of effecting this economy. The initial phase of the work as described here deals with a heat treatment of crushed raw ore, followed by thermal shock in cooling, for the preparation of rod mill feed. Several investigators1-" ave noted an improvement in the grindabilities of ores treated in this manner. One investigator2 subjected low grade iron ores to heat treatment in an electric furnace. Basing his conclusions on screen analyses of crushed products, he observed that treated ore was more easily crushed than the untreated. He reported that observation of the treated and untreated ore through a microscope revealed cracks following the grain boundaries in treated ore, whereas no cracks were present in untreated ore. However, few if any have quantified the improvement in terms of total hp hours saved, reduction of wear of grinding media, or reduction of capital costs of grinding equipment involved. By means of Bond rod mill and ball mill grindabilitiesh nd by comparative wear tests, the conditions maintained during this investigation have been definitely evaluated. Heat treatment experiments have been made on a batch scale in a muffle furnace, followed by continuous scale experiments in a rotary kiln under various conditions of temperature, atmosphere, retention time, and quenching to determine the combination that would give the greatest improvement in the grindability of a taconite without affecting adversely the magnetic susceptibility of the magnetite. From these data, relative costs have been calculated for grinding both untreated and heat- treated ore on a basis of plant capacity of 120 tons per hour. Heat requirements for a rotary kiln, as well as the kiln capacity required for the treatment, have been estimated. For these tests 50 tons of ore were obtained from the Aurora mine of the Erie Mining Co., Hibbing, Minn. The ore was reported7 to have been selected from the magnetic portion of the lower chert horizons. An average chemical analysis of' this portion is shown in Table I and an approximate mineralogi-cal analysis is shown in Table 11. No attempt was made to differentiate between the various silicates because the compositions vary widely on the different horizons and depend on the degree of oxidation. Minnesotite, however, is the predominant silicate. The siderite grains were dispersed throughout the ore but were essentially associated with the rock-forming minerals. In a series of preliminary tests in which batches of —6 mesh ore were heat-treated in a muffle fur-

Jan 1, 1953

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970