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By Ralph Wilcox

THE diamond drilling of certain characters of unstable rock forma-tion, as, for example, the copper-bearing schists of the Miami district in Arizona, is rendered most difficult by what is known as " caving" of the sides of the drill holes. As this caving is very greatly increased by the action of flowing water, it occurred to me, after experiencing a great deal of difficulty with caving in diamond-drill holes which I was drilling for the Miami Copper Co., that if I could substitute air for water, much of the caving-with resultant difficulties, such as decreased speed of sinking and increased consumption. of diamonds-would be overcome. After some experimenting, I found that it was perfectly practicable to substitute air for the water; forcing the air down the hollow rotating rods in the same manner as is done with water, the air passing out around the bit, which is thus cooled, and ascending on the outside of the rods to the collar of the hole, carrying the borings in just as satisfactory a manner as had been done by the water, but without the accompanying destruction or caving of the sides of the drill holes such as had been so generally experienced with the water. When water was encountered in the drilling this water was forced up to the collar just as it would have been had water been used in the .drilling, but with the correspondingly decreased flow there was relatively less washing or caving of the sides of the drill holes. The only change necessary in the arrangement of the drill is that a cross instead of a tee is used at the collar of the hole. A tightly woven jute bag is attached to one arm of the cross, for collecting and filtering the sample; and when drilling in dry ground a jet of water is attached to the opposite arm of the cross, to collect the dust and wash down the sample into the bag. The rods rotate through a stuffing box attached to the upper opening of the cross. The distention of the jute bag by the issuing air indicates the operating conditions as sufficiently as did the flow of water when using water in the drill hole.

Jan 10, 1913

By Charles Kirchhoff

For twenty years it has been my work to watch and record progress in both the technical and the commercial branches of mining engineering in the wide sense in which it is represented by our Institute. While you who have been actively engaged in our profession have made history, a few of us have attempted to be the historians and have been kept keenly on the qui vive to follow the developments of so broad a field. One so employed may be pardoned if he ask you to pause for the unusual purpose of looking backward, that you may measure what you and others have done, and that the younger men may gather inspiration from the work accomplished by their elders and their predecessors. It is not so long since that the commercial management dominated our industries. Bred in the school of science, which seeks its reward in establishing the truth, our engineers were sometimes indifferent to trade conditions and requirements. Much of that feeling has disappeared, and the engineer recognizes that it is his mission to apply the achievements of science to a useful commercial end. On the other hand, business men now understand that the utilization of our natural resources and the production of articles for consumption is impossible without the intervention of the engineer. They must co-operate, unless, indeed, the two functions are combined in one man —a rare but powerful combination. Now the final measure of success of both is the cost sheet on the one hand and the expansion of markets on the other, so closely interwoven, so mutually interdependent. There is one cardinal feature, however, which characterizes the engineer's work—namely, the permanence of his achievements. Every improvement, particularly when it has been recorded in such lasting form as a paper in the Transactions of our societies—

Jan 1, 1900

By W. L. Crentz, E. E. Donath, D. Doherty

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D0' " Elimination efficiency, in the terminology of Dahlstrom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By E. E. Donath, W. L. Crentz, D. Doherty

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D0' " Elimination efficiency, in the terminology of Dahlstrom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By E. J. Horwood

The varying physical character and large extent of the Broken Hill lode necesarily involve the employment of a variety of underground methods. The lode had its origin in an extensive fault plane traversing metamorphosed schists conformably, as a rule, with their beds of stratification. The underground waters carrying minerals in solution deposited their contents in the original cavities formed by the faulting action, and in the enlargements of these cavities due to dynamic forces brought to bear on the rocks, more especially on the hanging-wall side of the fault. This deposition was supplemented by metasomatic replacement of a portion of the original rock contents by the argentiferous sulphides of lead and zinc which form the staple products of the district. Although the orebody is practically continuous throughout the mines, its width varies greatly, ranging from a few feet to about 350 ft. The widest portions occur in conjunction with huge folds in the inclosing country rock, almost exclusively on the hanging-wall side. The ore in these folds pitches to the south in the southern half of the field, and to the north in the northern half; there are, however, undulations in these ore channels evidently due to compression of the rocks in the direction of the channels. In the earlier days, before the orebodies had been opened up, vertical cross-sections across these bulges in the hanging wall gave the lode the appearance of the "saddle formation," so well exemplified at Bendigo in Victoria; but subsequent development of the ore channels has long since proved that the formations in the two districts are entirely different. The depth reached by the zone of complete oxidation of the sulphides varies from about 259 to 550 ft, from the original outcrop, while partial oxidation extends in places below the 1,000-ft. level. The result of oxidizing influences has been the production of ore of every grade of cohesive-ness, from that of dry sand to that of hard compact rock. The methods of mining followed in this field, and even in individual mines, are varied in accordance with the character of the ore. The general practice of the field is to sink vertical shafts, generally on the foot-

Jan 1, 1916

By M. J. Sinnot, J. C. Shyne

Low-frequency mechanical damping measurements were made to investigate internal friction in Fe-A1 alloys. The atomic ordering of the Fe-A1 system strongly influenced the stress-induced ordering internal friction. Magnetoelastic damping was also encounteyed and was shown to be reduced by the application of a static stress. THIS paper describes some damping experiments made on alloys of Fe and Al. Stress-induced ordering internal friction was measured with samples containing from 9.8 to 31.3 at. pct Al. Aluminum is soluble in a-Fe to about 50 at. pct and forms at least two long-range ordered structures, Fe3Al and Feu.' Stress-induced ordering internal friction is known to occur in many substitutional solid solutions, but few measurements of this damping effect have been made with alloy systems that have pronounced ordering tendencies. LeClair and Lomer developed expressions relating the relaxation strength of the damping process to the degree of atomic ordering and predicted that stress-induced ordering internal friction would be zero with complete ordering.' This concept was confirmed experimentally by Lulay and Wert using the system cd-Mg It is also consistent with the weak stress-induced ordering peaks observed in P -brass by Artman and in 16 wt pct Al Fe-Al by bert.' It was expected, therefore that the ordering characteristics of the system Fe-Al would strongly influence the stress-induced ordering internal friction exhibited by the experimental alloys. SAMPLE PREPARATION The alloys used in this investigation were induction melted under vacuum using high-purity melting stock. The iron was electrolytically refined Plastiron 101 which contained 99.85 wt pct Fe. The aluminum was a special 99.95 pct pure grade supplied by Alcoa. The only other raw material was spectrographically pure graphite which was used in small quantities as a deoxidant. The amount of carbon used was slightly in excess of the amount required to completely deoxidize the melt; this resulted in residual carbon contents of 0.01 to 0.02 pct in the finished alloys. The vacuum cast 2 1/2-in. diam ingots were hot rolled to 5/8-in. diam round bars. Portions of these bars were hot swaged and hot drawn to 0.050-in. diam wire. Straight pieces of the hot drawn wire were slowly heated to a temperature of 1300°C in a He atmosphere. After holding for 4 hr, the samples were allowed to cool in the furnace. This annealing treatment resulted in grain growth in the samples, the final grain size being about the same as the wire diameter. The grain boundaries were oriented perpendicularly to the wire axis, giving a bamboo grain structure. The existence of a preferred orientation could not be detected in these coarse grained samples. If the samples had a fiber structure, this probably would have been the same in all samples because of similar processing, thus the influence of crystal orientation on the relaxation strength would have been similar in all samples. The aluminum contents of the alloys are listed in Table I. EQUIPMENT The principle of the torsion pendulum was used for the internal friction measuring device. The

Jan 1, 1961

By Richard Miller

WORK was undertaken two years ago at the Hammond Laboratory for the purpose of determining the magnitude of the elastic range in single crystals of pure metals by means of creep tests, the assumption being made that if a true elastic range exists, the elastic limit represents the maximum stress for no creep. A sensitive extensometer was constructed, and creep tests were made on zinc single crystals at a variety of loads and temperatures1. It was soon discovered that there is tip measurable elastic limit in ductile zinc single crystals at, or above, room temperature. The inference that pure metallic single crystals may not possess a definite elastic range was not justified, however, since zinc had been tested in creep only above its recrystallization temperature, and several investiga-tors2,3,4 had already shown that above the recrystallization temperature polycrystalline metals will flow under very small stresses, while below that temperature stresses of a much larger magnitude are required. For that reason, it was decided to extend the study of the elastic limit to other metals having a higher recrystallization temperature than zinc. Aluminum and silver were selected, because of the ease of obtaining pure materials and of preparing large single crystals, and because the crystallo-graphic glide system of these metals is well known. Owing to the limited time available, the elastic range was investigated by slow tensile tests rather than by creep tests.

Jan 1, 1937

By K. A. Natarajan, I. Iwasaki

Platinum electrodes are not inert as often thought to be. The reactivity of platinum electrodes can explain their erratic behavior in many electrochemical measurements of metallurgical interest, e.g, in flotation systems, streaming potential measurements, contact-angle measurements, and in leaching systems. The anomalous behavior of platinum electrodes in redox potential measurements in aqueous systems was studied through Eh and pH measure ments in water-oxygen, iron-water-oxygen, and manganese-water-oxygen systems. Stability relations between Fe++ and Fe (OH), and between Fe (OH), and Fe (OH), were studied to judge the correspondence between experimental and theoretical equilibrium lines. The practicality of redox potential measurements in estimating ferric-ferrous ratios in aqueous systems was investigated along with their suitability as indicators in leaching operations, e.g., the removal of iron by aeration from manganese leach solutions. Platinum electrodes have often been used in the measurement of dissolved oxygen concentrations and of redox potentials (Eh) in a variety of fields, e.g., analytical chemistry,' corrosion," geology and mineralogy,,'' biology,"' sewage treatment,' * hydrometallurgy,"I" and flotation."la The effectiveness of Eh-pH diagrams, first reported by Pourbaix' in 1949, has contributed much towards the theoretical understanding of numerous problems encountered in the metallurgical industry. Not many references are available in the literature, however, wherein attempts have been made to confirm Eh-pH diagrams from experimental measurements. One reason might be that, in spite of the apparent simplicity of the electrochemical technique, the direct measurement of Eh involves complex practical problems.' Factors such as the purity of the solution, the type of electrodes used, the history of the indicator electrode, and the type of atmosphere (namely, oxidizing, reducing, or inert) do have effects on the measured Eh values. The influence of mixed potentials cannot be underestimated. The poisoning of platinum electrodes by organic and inorganic impurities present in the solution may lead to erratic results. Platinum, commonly thought to be an inert electrode material, is not really so, as attested by a number of previous investigators who advised caution concerning the anomalous behavior of platinum electrodes in various electrochemical measurements.'" In the present article, a few pertinent experiments related to Eh-pH measurements in systems of interest in the metallurgical and water pollution fields are described in an attempt to correlate such information with what is already known, especially in the electrochemical literature. Iron-water and manganese-water systems were selected with a view of studying the correspondence between experimentally observed and theoretically established equilibrium lines. The work included an investigation of the behavior of platinum electrodes with respect to pretreatment and adsorption characteristics, the measurement of dissolved oxygen concentrations and their relation to Eh, the determination of the electrode potential of the ferric-ferrous couple at different pH, and the measurement of oxidation potentials in iron-manganese leaching systems. Experimental Procedure A rotating platinum electrode was used in many of the measurements to study the effect of rotation on measured Eh values. The electrode made by the Pine Instrument Co. consisted of a stainless steel rod with a platinum disk soldered to the end. It was covered with a Teflon insulation along the sides, so that only the circular tip of the electrode was exposed to the solution. Prior to its use, the platinum surface was brightened on a metallurgical polishing wheel with alumina as an abrasive, unless specified otherwise. The electrode was rotated with a Sargent cone-drive motor at 350 rpm. The contact of the electrode with the external circuit was made by filling a notch at the top of the stainless steel shaft with mercury and by dipping a copper wire into the mercury pool. The performance of the rotating platinum electrode was compared with the performances of a Beckman platinum button electrode and a platinum wire electrode. All the potentials were measured with respect to a saturated calomel electrode. A saturated KC1-agar bridge was used to minimize the liquid junction potential. A Beckman Zeromatic pH meter together with a Beck-man electrode switch was used to measure both the Eh and pH. A double-walled, all-Pyrex jar with a capacity of about 1 liter and themostated by circulating water of constant temperature was used for a reaction cell. Four equally spaced ports in the cover provided access for a glass electrode, a salt bridge connecting the saturated calomel electrode, a dispersion tube for bubbling gases into the cell solution, inlet and outlet tubes for passing the desired gases over the solution, and a graduated burette for introducing reagents from outside. The rotating platinum electrode was inserted through an opening in the top-center of the cover, and a positive gas pressure was maintained inside the cell to prevent air from entering into the cell compartment. A magnetic stirrer was used to mix the solution inside. For the determination of dissolved oxygen in the test solutions, the polarographic techniquex was used.

Jan 1, 1971

By L. D. Jaffe, J. H. Hollomon

The effect of tempering temperature and time upon the properties of quenched steel is clearly a subject of great practical importance, as well as of considerable theoretical interest. It would be very desirable to be able to predict the properties of a quenched steel when given any selected tempering cycle, with a minimum of experimental work upon that heat or even type of steel. Two problems are involved: one consists of relating the structure obtained to the physical properties, and will not be discussed here; the other, with which this paper deals, involves the relations of time, temperature and composition with the structure obtained 011 tempering. Indentation hardness is perhaps the most convenient quantitative measure of the tempered structure, or of what might be called the "degree of tempering." Undoubtedly, it is not an exact measure, and in some cases (as when temper-brittleness occurs) pieces of the same quenched and tempered steel may have widely differing properties at the same hardness. However, hardness has the advantage of being simple to determine and is certainly the most widely used indication of the degree of tempering. Moreover, for fully quenched steels that are not temper-brittle and do not contain retained austenite when quenched, it appears that, in general, if the hardness of the steel is the same, the tensile and impact properties will also be identical, whether a high or a low tempering temperature is used. The tempering charts available in the metallurgical literature usually give the hardness as a function of tempering temperature for only one tempering time. However, in practice, tempering times frequently vary, and a method of converting tempering curves for one time to tempering curves for some other time would be very valuable. It is also advantageous, in determining the tempering treatment necessary for a given part, not to have to temper samples at several temperatures for the time used for the commercial tempering operation. A more satisfactory procedure would be to employ times of the order of 10 to 30 min., rather than 5 or 10 hr., and if possible to use only one temperature. Furthermore, it is frequently desirable, for reasons such as temper-brittleness,* to obtain a given hardness with short times at relatively high temperatures, and it would be convenient to be able to compute without tests the time required to produce this hardness. Remarkably few quantitative studies of the hardness of quenched steel tempered over wide ranges of temperature and time

Jan 1, 1945

By W. M. Fox, D. P. Detwiler

IN the course of research on semiconducting inter-metallic compounds, it became necessary to obtain gallium metal of greater purity that that available commercially. Several methods were considered for further purification, including acid leaching,' fractional crystallization,' and zone-refining.3-5 The method of fractional crystallization was discarded as being equivalent to zone-refining in purification but inefficient in material and time. Both acid leaching and zone-refining were tried, and the method finally adopted is a combination of the two. The acid leaching technique has been reported' to produce gallium in which no impurities are detectable spectroscopically. Although this method is very effective in removing oxides and surface contaminants, semiconducting material made of gallium subjected only to leaching indicated little reduction in the concentration of metallic impurities. Zone-refining, however, appears very effective in removing trace metallic impurities, but comparatively ineffective in removing the surface oxide film. Consequently, the method evolved consists of acid leaching to thoroughly clean the surface, followed by zone-refining to remove metallic impurities. The low melting point and relatively high thermal conductivity of gallium introduce some difficulty in maintaining frozen and molten zones in zone-refining. To accomplish this, it is found necessary to reduce the effective ambient temperature by circulating ice water in coils about the regions that are to be kept frozen, while heat is supplied to the molten regions by resistance coils. The power supplied to the heating coils is regulated by a constant-voltage transformer and a variable autotransformer. Both heating and cooling coils are mounted on a transite base. The gallium ingot is held in a closed pyrex tube sliding inside the heating and cooling coils, the reciprocating method of Tanenbaum et al. being employed to move the molten zones through the ingot at a rate of 2 in. per hr. This apparatus is shown in Fig. 1. The results of a spectroscopic analysis f a zone-refined ingot, as well as of the material as-received and after acid leaching, are shown in Table I. The ingot was 32 cm in length, and received 37 molten-zone passes, the molten zone being about 4 cm long. The only impurity found was lead, the following elements being reported also as checked but not found in the pure material: Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cb, Cu, Ge, Au, Fe, Mg, Mn, Mo, Ni, Pt, Si, Ag, Na, Sr, Sn, Te, Ti, W, V, Zn, and Zr. There thus appears no indication of pickup of Al, Mg, or Si from the pyrex boat as reported by Zimmerman' in his fractional crystallization. Thus it appears that definite removal of lead from gallium occurs during the zone-refining process. It also may be concluded that a more sensitive analytical procedure than spectroscopy is required to evaluate quantitatively the purity of zone-refined metals. One such procedure which is proposed for use in the near future is the measurement of very low temperature resistivity. Although this will not identify the impurities present, it offers a very sensitive check of total impurity. Acknowledgment This work was supported by the Air Research and Development Command, United States Air Force.

Jan 1, 1956

By A. R. Krause, C. Laird

In order to establish whether or not there is a real temperature effect in fatigue (independent of environment) , poly crystalline copper and Cu- 7.9 A1 alloy have been cycled at 298° and 7° K in vacuo and the fatigue lives compared with those in air and in liquid nitrogen. The lives of both copper and the alloy were found to be highly temperature-dependent in the absence of environment. This result casts serious doubt on the validity of the cell structure hypothesis for stage I crack propagation as presently formulated, because it predicts that there should be no such tempevnture dependence. On the other hand, the plastic blunling process is consistent with the result. Effects of environment aside, the homogenization of slip which accompanies testing at low temperature, and at low strains, seems to be the main cause for increased fatigue life. At high strain amplitudes, the fatigue lives of wavy slip materials, typically copper, are independent of temperature.' It is well-known, however, that low-strain lives greatly as as the temperature of testing is decreased. By contrast, the lives of planar slip materials, such as Cu-7.9 pct A1 alloy, increase to an even greater extent with decreasing temperature throughout both the high and low strain ranges.1'2'5 The mechanism of this temperature effect is associated with the earliest stages of fatigue failure,'" crack nucleation, and stage I growth,"' which is slow propagation along slip bands to the depth of a few grain diameters. Such life behavior has been interpreted on at least two different bases. On the one hand, those interested in the temperature effect at high strain amplitudes1 believe that stage I growth occurs by the plastic blunting process of crack propagation.7'9 They explain the effect in planar slip materials by the homogenization of slip* which accompanies fatigue testing at low temper- atures and serves both to delay crack nucleation and to decrease the rate of stage I propagation. On the other hand, Holt and Backofen,2 who have studied the effect in low strain fatigue, believe that stage I growth can be interpreted by a cell structure hypothesis.10-12 They have challenged2 the conclusion that there is a real temperature effect in this regime of fatigue testing and have interpreted the increased fatigue lives almost entirely in terms of the "environmental-protective'' effect of the liquid nitrogen and helium baths used to obtain low temperatures. This interpretation by Holt and Backofen2 may offer a means of discriminating between these two mechanisms as currently formulated and used to explain stage I growth. On the basis of the plastic blunting process applied to stage I crack propagation,7* the low strain fatigue lives of both wavy and planar slip materials should be increased with decreasing temperature. This follows because both materials show increased slip homogenization in this strain regime."13 Consequently, crack nucleation in intensified bands will be delayed and the linking of such small cracks into larger stage I cracks will be difficult. In addition, the blunting process required to lengthen a stage I crack from the order of 2 to 10 (where the strain concentration of the crack begins to overcome the slip homogenization property of the material) will also be retarded. These delays will give rise to longer lives in both kinds of material. In contrast to the blunting hypothesis, no temperature dependence has been predicted on the basis of the cell structure hypothesis, because it is well-known that materials cycled at low temperature show no differences in type of dislocation structure for a given strain amplitude.18"20 If the lives of wavy and planar slip materials do show a temperature dependence when the environment is eliminated as a variable, then it is questionable whether cell structures per se have a fundamental role in fatigue fracture. Accordingly, specimens of copper and Cu-7.9 wt pct A1 have been cycled at 298° and 77°K in vacuo and the fatigue lives compared with those in air and in liquid nitrogen, in order to establish whether or not there is a real temperature effect in low strain fatigue. Since it is difficult to measure the strains in specimens when cycled in vacuo, S-N curves have been used as the basis of comparison. In studying the influence of temperature on fatigue life in ordinary environment, Holt and Backofen2 used the superior basis of E-N curves. However, they also published S-N curves and thus established the relationship between E-N and S-N curves. This relationship is used to support the S-N comparison reported in the present investigation. EXPERIMENTAL Materials. The copper employed in this investigation was of 99.99 pct purity and the cu-7.9 pct A1 was prepared from metals of the same purity. The stock, of 3 in. initial diam, was reduced in size by rolling

Jan 1, 1969

By J. J. Kramer, G. W. Wiener, K. Foster

The effects of the primary grain size and sheet thickness on the secondary growth rates of grains with (100) surface planes were studied in 3 pct Si-Fe sheets. This secondary grain growth was carried out under conditions in which the {100} plane had the lowest surface free energy. The value of the surface energy difference, between the (100) plane and the random matrix planes was found to he only about 3 pct of the grain boundary energy, indicating that most of the driving force for secondary growth is supplzed by grain boundary energy. A method for obtaining cube texture in 3 pct Si-Fe sheets by a secondary recrystallization process has been reported.' It has been demonstrated that a difference in surface free energy between the (100) plane and other planes is responsible for this growth, where the (100) plane has the lowest surface energy. A semiquantitative relation has been derived for secondary grain growth in sheets where primary grain growth has proceeded until the grains have grown through the sheet and the average grain diameter in the plane of the sheet is from one to two times the sheet thickness. Then, the linear growth rate, G, for the secondary grains can be given by where M is the grain boundary mobility, is the grain boundary free energy, is the average primary grain radius, A is the average difference in surface free energy between the (100) plane and planes of other orientations, t is the sheet thickness, and C is a term first proposed by zener6 which acts as a negative driving force, the effect of inclusions in holding up grain boundary motion. Since the problem of grain growth being discussed is under conditions where the matrix grain size is at least equal to the sheet thickness, the radius r is, of course, a function of the sheet thickness. The term B/r is the grain boundary driving force normally associated with inclusion inhibited or texture inhibited secondary recrystallization. Here, however, the term is modified to account for the fact that growth occurs in thin sheets. The term is the additional driving force available because of the difference in surface free energy. The purpose of the present work has been to evaluate the driving force terms of the growth equation by studying growth rates of (100) secondary grains as a function of sheet thickness and primary grain size. From these data it has been possible to determine the relative values of grain boundary energy, surface energy difference, and the inclusion term, C. EXPERIMENTAL PROCEDURE A 3 pct Si-Fe alloy was melted and cast under a helium atmosphere using electrolytic iron and a pure commercial grade of silicon as raw materials. The alloy was hot and cold rolled to a thickness of 0.6 mm, and samples approximately 5 in. long by 1 1/4 in. wide were cut from the cold-rolled sheets. Four different primary grain sizes were obtained

Jan 1, 1963

By J. L. Wyatt

J. W. Tomlison—It seems probable that the author's conclusion, that the conductivity of the slags decreases with increasing content of FeO, is erroneous due to the method of plotting the data. Thus, the results of other workers2,3,13,14 show that the conductivity of molten oxide slags increase with increasing temperature, indicating that the trend of the curve shown by the authors is due to the fact that the data for the slags containing relatively small amounts of FeO are at higher temperatures than those for the slags containing relatively large amounts of this oxide. In this connection the work of Wejnarth2 may be mentioned in which in an investigation of a series of iron silicate slags, the conductivity was found to increase with increasing content of FeO; the fact that the author's slags contained TiO2 probably does not affect the issue since it has been shown15,16 that, at least as far as conductivity is concerned, this oxide behaves essentially the same as silica and that mixtures of the oxide with silica have a very low conductivity of the order of 10-4 mhos at 1750°C. In connection with the experimental technique it may be noted that bubbles of carbon monoxide would probably be produced at the surface of the graphite electrodes in contact with the melts thus rendering the accuracy of the measurements somewhat open to question. J. L. Wyatt (author's reply)—Dr. Tomlinson makes reference to works by Martin and Derge, which indicate that slag systems containing no TiO2 are charac-terized by an increase in conductivity with an increase in temperature. Further, I have cited his examples, which indicate a drastic increase with small temperature change. The results of Dr. Derge's work have no bearing whatsoever on the results of this paper, since the slags under study here contained up to 70 pct TiO2. One cannot generalize on slag systems as a whole on the basis of any one family, for there are definite compounds of ionic nature formed in each system, and the ionic mobilization of these is something that cannot be determined without actual experimentation. Dr. Tomlinson makes reference to an unpublished work which, he claims, shows that titanium dioxide behaves the same as silica in regard to conductivity. Since I have not had 'an opportunity to see the paper I cannot make any comments, but unless the same slag system was studied there can be no specific comparison of results. If the decrease in conductivity of the slag was due entirely to temperature phenomena, as Dr. Tomlinson indicates, then one is without an explanation of the values shown in the paper for slags containing from 10 to 20 pct FeO. I cannot agree that the deviation in findings was appreciably related to temperature change; further, I believe this point was completely covered in the paper. References 13 Endell and Hellbrügge: Glasstech. Ber. (1942) 20, 277. 14 Bockris, Kitchener, Ignatowicz and Tomlinson: Faraday Society. Discussion (1948) 4, 265. 15 Tomlinson: Thesis, London 1949. 10 Bockris, Kitchener, Ignatowicz, and Tomlinson: Unpublished work.

Jan 1, 1951

By R. M. Douthwaite, G. Birkbeck

The effect of grain size and specimen dimensions on the occurrence and magnitude of a yield point drop in pure iron has been examined. The tests were done at room temperature. The results indicate that gain size is the critical factor determining whether a yield drop occurs. The specimen diameter:gain size ratio does not influence the magnitude of the yield drop for the range of gain size and specimen diameters investigated. HUTCHINSON,' petchY2 and worthington3 have investigated the grain size dependence of the upper yield stress (uUYP) and the yield point drop, ouyp - aLYP, in Armco iron, mild steel, and Si-Fe, respectively. These authors used center-annealed wires to avoid stress concentration from specimen shoulders and to ensure uniformity of the applied stress. Coarsegrained specimens show no yield point drop; the yield point drop then increases as d-'I2 increases (where d is the grain diameter). These results can be understood in terms of Petch's analysis2 in which the magnitude of amp depends on the strain rate in the (limited) number of grains deforming plastically at the upper yield point. If N grains per unit volume are undergoing plastic deformation, the strain rate in the deforming grains is l/Nd3 times higher at the upper yield stress than when the whole specimen deforms homogeneously. If N is constant and independent of grain size at uUyp, then all the grains are deforming when ~d~ = 1, so there is no yield point drop. At finer grain sizes, the yield point drop is given by: where AU, is the friction stress increase corresponding to a tenfold strain rate increase. Christ, Smith, and Burton studied the upper yield point in 0.050-in.-diam wire specimens prepared from zone-refined iron. Each end of the 2; -in. specimens was soldered to a & -in. diam steel ball and the load applied through the two balls. There was a yield point drop in specimens with grain diameters less than 0.1 mm; no drop was observed in specimens of grain diameter greater than 0.1 mm that were free from veining substructure, but specimens of grain diameter 0.129 mm, annealed in the y range, showed an upper yield point. and this was associated with the presence of a veining substructure in these specimens. Christ et al. suggested the upper yield point occurs when more than a specific number of grains fill the specimen cross section so a multiplicity of slip is required to initiate plastic deformation. Table I summarizes the published data on the grain size at which the yield drop disappears. On the basis of this data the ratio of specimen diameter:grain diameter = 5 to 27 appears to be the critical value for the occurrence of a yield point drop. Thus, petch2 interprets the appearance and magnitude of the yield point drop in terms of the limited number of grains deforming plastically at uuyp, whereas Christ et a1. consider that the occurrence of the yield drop depends on the ratio specimen diame-ter:grain diameter. The published data cover a wide variety of materials so some variation between the results is to be expected, but the size range covered in the data of Table I is rather limited. In an attempt to discover whether the specimen diameter:grain size ratio or the grain diameter is critical in determining

Jan 1, 1969

By Wei-Kao Lu, G. Bitsianes

An improved general rate equation for a one-ditnensional gas-solid system has been derived. Fov the veversihle interfacial chemical reaction, there are concentrations of gaseous reactant and product at the reacting zone to be considered. They have been calculated with the velations fuvnished by the constraints on the system, namely, quasi-steady state and equimolal counterdiffusion of the gases. The results of the diffusiori study of Evans, Watson, and ,Mason based on the "dusty gas" model have been applied here. The interfacial chemical reaction is taken as first-order with respect to the concentration of the gases involved. The equation has proper dependence on gas composition and on solid structure through the relative values of Knudsen and normal diffusivities. The existence of the total pressure gradient inside the specimen has been predicted and confirmed experimentally. In a previous communication' we introduced a general rate equation for gas-solid reactions by considering the contributions of chemical reaction at inter- phase boundaries and diffusion through the solid product layer simultaneously. These equations, for one-dimensional and spherical specimens, take care of the whole range continuously from purely diffusion control to purely chemical reaction control. In this paper we study only the one-dimensional system. The corresponding rate equation is reproduced here: Of the two terms on the right-hand side of Eq. [I], the first represents the contribution of interfacial chemical reaction and the second that of gaseous diffusion. The shortcomings of Eq. [I] are that in its derivation the interfacial chemical reaction was assumed to be irreversible and the diffusion rate of gaseous product was not considered. Any pressure effects building up within the porous media were also neglected. Evidently. these simplifying assumptions will limit the general applicability of these equations. The rate of reduction of iron oxide by hydrogen, for instance, is very sensitive to the concentration of water vapor in the main gas stream, as has been reported by cewan' and by Quets et a1.3 Furthermore, the gaseous phase at the reacting interface will contain an appreciable amount of the gaseous product of reaction. If this were not true, a sufficiently high concentration gradient for the outward diffusion of the gaseous product could not be maintained. With these shortcomings in mind, Eq. [1I cannot be rigorously ap-

Jan 1, 1967

By D. B. Robinson, C. A. Macrygeorgos, G. W. Govier

Experimental data have been obtained on the volurrletric behavior of ternary mixtures of methane, hydrogen sulfide and carbon dioxide at temperalures of 40°, 100" and 160°F up to pressures of 3,000 psia. The results indicate that the compressibility factors for this system do not agree with compressibility factors for sweet natural gases at the same pseudo-reduced conditions. The deviation increases as the temperature and methane content decrease. Discrepancies of up to 35 per cent were observed. A careful analysis has been made of the existing pUrblished data on compressibility factors for binary systems containing light hydrocnrbons and hydrogen sulfide or carbon dioxide. It has been found that the deviation of actual from predicted compressibility factors for methane-acid gas mixtures is a function of the methane content and the pseudo-critical properties,.v of the mixture. The ratio between actual compressibility factors for methane-acid gas mixtures and compressibility factors for sweet natrlral gases at the same pseudo-reduced conditions has been currelated over a range of pP,, from 0 to at least 7 arid a range of pT, from about 1.15 to at 1east 2 0 with an error not exceeding 3 per cent and over most of the range within I per cent. The validity of the correlation for mixtures containing appreciable hearvier hydrocorbons has not been fully established, but it is shown to be preferable than the use of a corretation based only on hydrocarbons. INTRODUCTION Although a relatively accurate method for predicting compressibility factors of pure materials is provided by charts based on reduced properties and the assumption that the compressibility factor is a unique function of T P and z the determination of the correct values of compressibility factors for gas mixtures is somewhat difficult. Two general methods of dealing with gaseous mixtures have been proposed. The first assumes a direct or modified additivity of certain properties of the mixture in terms of the properties of the individual components. Examples of this method are based on the familiar laws of Dalton and Amagat. The second method averages the constants of an equation of state applicable to the pure components. Both of these methods are of limited value in engineering calculations because the first usually provides reliable answers only over narrow ranges of pressure and temperature and the second is cumbersome to handle. In petroleum engineering practice accurate estimations of the volumetric behavior of natural gases arc frequently required. To fulfill this need, several generalized compressibility charts have been developed.' ' Of these, the one prepared by Standing, el al is widely used at present. In the construction of charts of this type a third method for dealing with mixtures has been followed. It is based on correlation of pseudo-critical properties as outlined by Kay and calculated from the critical properties of the individual components in a mixture. Although these charts provide relatively accurate information on the compressibility of dry or wet sweet natural gases, they are less reliable when used for gases containing high concentrations of hydrogen sulfide or carbon dioxide or both. Thus, an experimental program, although time consuming, is the best means now available for the determination of the volumetric behavior of sour or acid gas mixtures. An increased interest in the behavior of these gas mixtures, particularly in connection with some of the fields in Western Canada where the acid gas concentration of the reservoirs may be as high as 55 per cent and where hydrogen sulfide alone may be as high as 36 per cent, provided the incentive for this study. It was the purpose of the investigation to determine the volumetric behavior of selected mixtures of methane, hydrogen sulfide and carbon dioxide over a range of temperature from 40" to 160°F and at pressures up to 3,000 psi. EXPERIMENTAL METHOD The apparatus used in this investigation was basically the same as that described by Lorenzo.'" The amount of each pure component used in preparing the gas mixtures was measured over mercury in a glass-windowed pressure vessel. The pure components were then transferred individually in the desired amounts to a second glass-windowed pressure vessel where the volumetric behavior of the mixture was determined. Volume was varied by mercury injection or withdrawal. The capacity of the cell was about 125 cc. Temperatures in the cells were measured with copper-constantan thermocouples and a Leeds Northrup semi-

By H. C. Fiedler

Heats of high purity iron containing 3.1 pct Si and be -tween 0.0003 and 0.0295 pct N were prepared by vacuum melting ad then pouring while in a nitrogen atmosphere with the pressure between 0 and 90 psi. Strip from a heat with 0.0184 pct N underwent complete secondary recrystallization during the final anneal. Heats with less nitrogen had too few Si3N4 particles to restrain normal grain growth, and the heat with higher nitrogen had too many particles to allow complete secondary recrystallization. In the hot-rolled structure, Si3N4 precipitates only at the grain boundaries, with the consequence that annealing after hot-rolling diminishes the ability to subsequently undergo secondary recrystallization. In contrast to this behavior, ALNprecipitates uniformly in the hot-rolled structure. Under 1 atm of nitrogen, Si3N, in 3.1 pct Si-Fe dissociates between 900" and 950°C; the solubility of nitrogen increases from 0.0010 pct at 900" to 0.0030 pct at 1200°C. The solubility of nitrogen in Si-Fe has been the subject of many investigations. Corney and Turkdogan1 heated a 2.83 pct Si alloy in nitrogen and found the solubility, under 1 atrn of nitrogen, to be 0.0019 pct at 900°C. They claimed that Si3N4 did not form in the alloy above 705°C in 1 atrn of nitrogen. Fryxell et al.2 heated samples of 3.25 pct Si-Fe containing 0.0025 pct N over a range of temperatures and then analyzed for total nitrogen by vacuum fusion and for nitrogen in solution by a modified Kjeldahl technique. At 900°C, they reported the solubility of nitrogen in equilibrium with Si3N4 to be 0.0011 pct. pearce9 found the solubility of nitrogen at 900°C under 0.95 atrn of nitrogen to be 0.0017 pct in a 3.06 pct Si alloy. He reported that Si3N4 does not form above 770°C in 1 atrn of nitrogen. Although internal friction measurements have given somewhat higher values for the solubility,4-6 if the solubility of nitrogen is as low as has been reported by most investigators, and if Si3N4 is stable up to at least 945°C at 1 atrn pressure of nitrogen as reported by Seybolt,7 a small amount of nitrogen in properly processed Si-Fe should be effective in promoting secondary recrystallization. The requirement is that in the final heat treatment there be enough small, well-dispersed particles of Si3N4 to restrain normal grain growth. Fast8 has obtained secondary recrystallization by nitriding high-purity 3 pct Si-Fe after hot-rolling to a thickness of 0.118 in., followed by processing to 0.012 in., and annealing. A large amount of nitrogen, 0.076 pct. was introduced during the nitriding heat treatment, but he has since reported9 that "a few hundredths of a percent" is sufficient. Small amounts of aluminum10 or vanadium" nitride are capable of promoting secondary recrystallization. Heats containing as little as 0.010 pct A1 or 0.042 pct V and from 0.006 to 0.009 pct N underwent complete secondary recrystallization at final gage, whereas heats with lesser amounts of aluminum or vanadium did not.l2 To be reported is the behavior of nitrogen in high-purity 3.1 pct Si-Fe, and the relation of this behavior to the ability to undergo secondary recrystallization. PROCEDURE Ingots weighing 1 lb were made by vacuum melting high-purity electrolytic iron (A104, Glidden Co.) and high-purity silicon (Monsanto Co.). The latter was used in preference to ferrosilicon to insure a low aluminum content. The design of the melting furnace permitted pouring with the furnace atmosphere either below or above atmospheric pressure. Accordingly, at the completion of melting, nitrogen was admitted to the desired pressure and the heat then immediately poured. The ingots were sound, with no indication of porosity. In Table I are listed the heats investigated, the nitrogen pressure at pour, and the nitrogen and oxygen contents as determined by vacuum fusion with a platinum bath at 1850°C, a procedure which insures measurement of the total nitrogen.13 In addition, all heats contained 3.1 pct Si and not more than 0.002 pct C, 0.003 pct S or 0.005 pct Al. It was subsequently found that the quantity of nitrogen contained in the heats in Table I does not necessarily represent that obtained under equilibrium conditions. For example, the ingot poured immediately after 1 atrn of nitrogen was admitted to the chamber contained 0.0093 pct N, whereas an ingot poured 3 min after the nitrogen was admitted contained 0.021 pct N and another poured after a 6-min delay contained 0.029 pct N. While some bleeding of the hot top occurred in the latter instance, the ingot when examined in cross section appeared sound. The ingots were heated to 1325°C in hydrogen and rapidly rolled to 0.080 in. in 3 passes. The roll speed of the final pass was reduced so as to increase the quenching effect of the rolls. The hot-rolled pieces were processed both as-hot-rolled and after heating for 3 min at 900°C in hydrogen. After cold-rolling to 0.026 in., the strips were heated for 2 min at 900°C in hydrogen, then cold-rolled to the final gage of 0.012 in. The loss of nitrogen in going from the ingot to cold-rolled strip was no more than 10 pct. The final heat treatment, which was for the purpose of develop-

Jan 1, 1970

THE TRANSACTIONS of the Institute for the early years display but Little interest in physical metallurgy-indeed, it is striking how thoroughly process metallurgy absorbed attention until quite recent years. The first volume carries no article that can be strictly described as physical metallurgy, unless one on the rolling and hammering of ingots be doubtfully so described. Nor does the second volume contribute more the interest then was in mining, and in production methods, both ferrous and nonferrous, with much attention to the new methods of making steel. The third volume records papers on: the condition of carbon in gray and white iron, a paper devoted to chemical rather than microscopic analysis; the annealing of spiegeleisen; phosphorus and carbon in iron and steel, similarly chemical. Much attention was given, and continued to be given for years, to the manufacture and behavior of rails. The question of the nature of steel appeared early (Vol. 11)-What is Steel, by A. L. Holley-where arguments on nomenclature were already active; and Holley also bemoans, in modern spirit, the Inadequate Union of Engineering Science and Art; Pearse wrote on cast iron for guns (reflecting again the ironic beneficence of war in metallurgy), and said that Captain Walbach was the first to insist on chemical analysis of gun irons; he quotes Major Wade's study of comparative hardness, using penetration hardness measurements (Brinell was to come later), and quotes the important Reports on the Strength and Other Properties of Metals for Cannon, by H. C. Baird, Philadelphia, 1855, in which the advanced state of tensile testing at the time is shown. Hewitt, in Vol V, comments upon the function played by technical schools and technical societies upon the growth of metal-

Jan 1, 1948

By Leonard Austin

WHAT Colonel Dwight says regarding the treat-ment of oxidized ores1 holds true also of the silver-lead smelting operations in Utah. The ore sought for was such as would, with appropriate fluxes, yield slag, and "lead bullion," as the lead reduced from the ore and carrying its gold and silver, was called. No matte, and probably little or no speiss, was yielded, and hence there was nothing to roast, either of ore or matte. But, by 1880, when I first took hold in smelting, there was quite a production of matte at the works of the Ger-mania Smelting and Refining Co., Utah, because, by that time, ores containing some pyrite and galena were being smelted. This was due, as at the Grant Works, Denver, to the more attractive price paid for the treatment of such ores. The matte, containing about 5 per cent. copper, was accordingly heap-roasted and returned to the blast furnace for the recovery of its contained metals. By this time there had been built a long-bedded, hand-rabbled reverber-atory roaster with a hearth of about 40 by 10 ft. in size, and in this matte and ore, crushed at the sampling mill, was treated. When, in 1892, I took control of this works, called& now the Germania Lead Works, three other roasters had been added, but the prac-tice of heap-roasting continued. This had the merit of needing no equipment, and of doing good work, because the pieces that were imperfectly roasted went back upon the next roast heap. At this time, when some suitable lump ore was obtainable, I roasted in heaps, in a satisfactory way. By 1892, the Bruckner cylinder roaster had been installed, which, compared with the reverberatory roaster, reduced labor. As such a cylinder revolves, a talus of ore is formed within it and at the same time fresh surfaces are exposed to the air, but the trouble was that the air did not reach to the bottom of the cylinder. This we corrected by placing a steam jet at the fire-box end, to project the air down-ward upon this stagnant ore, thus increasing the speed and completeness of roasting without at the same time increasing dust formation. The firing, if skilfully done, gave a somewhat sintered product, but with certain ores a slight access of heat over the normal would cause accretions to form within the cylinder near the fire end. These could be cut off by running back the fire box and barring off the crusts. It was in 1895 that the Bruckner cylinders at the Arkansas Valley plant, Leadville, were giving unsatis-factory service and I was called in to investigate. The steam jet was put in use as at the Germania Lead Works, but we found that, due to the altitude (10,500 ft.), combustion was feebler than at sea level or even at 4000 to 5000 ft. Later it appears, as Colonel Dwight states, that R. D. Rhodes and Mots sought to increase the air supply by admission through perforated tiles, but the trouble was due to the air itself.

Jan 8, 1922

By T. S. Lundy, R. A. Padgett

The fact that cobalt diffuses in silver at a much slower rate in a region near a free surface than in bulk material has been demonstrated in a variety of experiments. Various possible mechanisms of this near-surface effect (NSE) are examined in light of experimental evidences. The tendency for surface segregation of some solute atoms appears to be a likely mechanism to explain the effect. UNIDIRECTIONAL and isothermal diffusion from a plane source of radioactive tracer into an isotropic, homogeneous medium follows the Gaussian solution to Fick's second law, or: where A(x,t) is the position and time-dependent concentration of the diffusing species, M is the quantity of diffusant per unit area initially at x = 0, and D is the diffusion coefficient. For a given time, say t = tl, one can easily see that: d In Aixji)_____1_ r2] d(x2) 4Dti Thus, if diffusion data obtained by serial sectioning are plotted as In A(x,tl) vs x2, the diffusion coefficient is obtained from Eq. [2]. The ideal behavior seldom is observed in real systems. Deviations from ideality generally occur either at small or large values of penetration distance. The overall picture is shown schematically in Fig. 1 where Regions I, 11, and 111 are due, respectively, to some near-surface effect or effects (NSE), volume diffusion, and short-circuiting effects. For different systems and conditions of specimen preparation and analysis, the relative importance of Regions I, 11, and I11 may be drastically different. Region I is completely absent in many systems and there is no NSE. In others, however, there may be considerable difficulty in determination of volume diffusion coefficients due to the overshadowing influences of Region I. Such is particularly true when indirect techniques such as the surface concentration decrease or the Gruzin method' are used to find D. In this paper several experiments which had as their goal a better understanding of near-surface effects are reported. Specifically, it is well-known that unusual penetration behavior results for the diffusion of several impurities in ilver- and that considerable controversy exists with regard to interpretation of the published diffusion data. We chose to examine those unusual results which occur for cobalt diffusion in monocrystalline silver395 primarily because knowledge of experimental procedures and materials were readily available. Both radioactive co60 and co5' could be utilized to offer a wide range of available concentration of the diffusing species. Experiments were also performed on the diffusion of AgnO in silver. They gave base-line data for the system—both for technique evaluation and for examination of the vacancy distribution near the surface. I) PROCEDURES Cylindrical-shaped specimens 1.25 cm diam and 1 to 1.25 cm long were cut from 99.999 pct Ag single crystals obtained from Monocrystals Co., Cleveland. One end surface of each specimen was polished flat and etched with a mixture of 20 ml saturated Cr03 solu-tion-20 ml H20-3 ml concentrated HC1. Radioactive tracer (co60 or co5' or Ag'lO, each having a radio-chemical purity of greater than 99 pct) was deposited onto the prepared surface either dropwise with evaporation to dryness of the solution containing the tracer (0.5 N HC1 solution for the co60 and co5' and 0.6 N HNO3 solution for the A"'), by electroplating, or by evaporation from a tantalum or tungsten filament in an evacuated bell jar. The amount of deposited cobalt was varied from many atomic layers of cobalt containing the co60 to approximately one co5' atom per lo6 surface atoms of silver. This large variation in amount of deposited cobalt yielded information about both the influence of a thick-source layer of tracer and solubility effects on the NSE. Such variations were possible because of the large differences in half-lives,

Jan 1, 1969