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By R. C. Urquhart, W. P. Channon, D. D. Howat

Discussion: The mode of current transfer between electrode and slag in the submBerged-arc furnace by w. P. CHANNON, R. C. URQUHART, and D. D. HOWAT J. MEINTJES I have read the paper with much interest, and I should like to make a few observations. (I) The experimental work deals with resistance heating by an electrode immersed in a slag... AUTHORS' REPLY We thank Mr Meintjes for his critical analysis and helpful comments arising out of his study of our paper. Possibly we should emphasize at the outset that our experiments all related to the conditions in which the lower portion of the electrode was immersed in molten slag. We believe, however,

Jan 12, 1974

DISCUSSION: The value of incentive payments in the mining industry by K; SMITH Published in the Journal, May 1974 H. P. CARLISLE* The author has drawn attention to one of the most important of mining problems, viz productivity, and in so doing has highlighted, perhaps inadvertently, the difficulty of assessing productivity. Competition for Students Each year the Institute offers a prize (or prizes should the entries warrant it) of up to R100 for the best paper or dissertation on a topic appropriate to the interests of the Institute. Corrigendum The Journal, May 1974, p. 377 We regret that the last portion of A. A. Hazell's contribution to the paper 'The value of incentive payments in the mining industry' by K. Smith was printed in the wrong sequence.

Jan 10, 1974

(SECRETARY'S NOTE.) The following discussion of the papers of Van Hise, Emmons, Lindgren and Weed, read at the Washington meeting, February, 1900, and printed on pp. 282 to 498 of this volume, comprises communications to the Secretary, received at various times before the Richmond meeting, February, 1901, and, for the most part, presented at that meeting. These communications are introduced at this point in the present volume, in order that they may precede the papers of Vogt, hemp, Lindgren, Rickard, etc., presented at Richmond, and therefore not forming part of the material considered in them. Since many of the contributors have mentioned in one communication several of the papers referred to, no attempt is here made to divide their remarks and distribute the fragments under separate headings. In each contribution, however, the several topics are indicated by subtitles. R. BECK,* Freiberg, Saxony : Prof. Veal Hise's Paper.-The paper of Prof. Van use (p. 282) represents a great step of scientific progress, in that the circulation of underground waters has never before been presented with such clearness, ill the light of modern chemical and physical knowledge. The theories of the formation of ore-deposits which follow the author's general survey of the currents and solvent power of atmospheric waters in the earth's crust do not, indeed, seem to be novel, being essentially an amplification of Le Conte's views; but the proofs adduced in their support are in many particulars so original that no one can read without profit this portion of the paper. Entirely new (though largely in agreement with the papers of Emmons and Weed, presented at the same meeting of the Institute) are the sections dealing with the formation of the rich sulphides of the precious metals, and especially the regeneration of normal sulphides, such as galena, etc., in vein-zones immediately beneath the ground-water level. Nevertheless, it appears to me that Prof. Van Hise, in the course of his most instructive exposition of unquestionable, yet still locally limited, phenomena, has been too much biased in favor of the " descensionists." This is indicated by the small importance which he attaches to the intimate genetic relation between epigenetic deposits and the plutonic hearths of the earth's interior.

Jan 1, 1902

The negative charges on diaphragms of quartz, tungstic oxides, stannic acid, acid dyestuffs, soaps, and glass have for a number of years been explained on the basis of chemical equilibria-a hydrogen ion or light metal ion passes into solution leaving the solid complex ion negatively charged. While there are a number of observations which indicate a proportionality between the ( potential and the streaming potential it should be recognized that all the experimental evidence thus far presented shows that if hydrogen ion concentration is kept at a constant value, electrokinetic phenomena are influenced by salts. The multivalent ions exert the greatest effect on the reduction of osmotic flow. In the interpretation of all electrokinetic data the assumption is made that the potential of the solid remains constant. That this is not true is evidenced by the values of ( potential for quartz in contact with conductivity water as reported by the several investigators and by the authors of this paper.

Sep 1, 1956

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 workers2,3,13,15 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 characterized 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

J. R. Lane (Metals Research Laboratory, Washington)—A new type of deformation called "kinking" has recently been described. Is there any relation between the "rumpling" described in this paper and "kinking?" D. C. Jillson (author's reply)—Both are manifestations of bending about [210] axis. The difference is one of degree. W. C. Ellis (Bell Telephone Laboratories, New York) —Some observations of deformation in zinc recorded in this paper may be applicable generally to flow in metals. One of these, deformation in torsion without evidence of slip or twinning in the early stages and with startling ease, when the twist is about the hexagonal axis, adds another method of flow to the presently increasing list of mechanisms. This illustrates again that a crystal will utilize any realizable process to flow and relieve stress. The process is not necessarily classical directional slip—& this case, it is rotational slip. The question naturally occurs: Will face-centered cubic metas stressed by twisting about an octahedral axis flow in a similar manner by rotation on an octahedral plane? I would like to ask Dr. Jillson if he has made any experiments or knows of any experiments of this type on face-centered cubic metals? Face-centered cubic metals possibly would behave differently from zinc, since, for one thing, the stacking sequence is different for the two structures. The results of such experiments, however, would be instructive in providing more information about deformation processes. D. C. Jillson—Dr. Roy E. Swift, working in the Hammond Laboratory at Yale, performed a twist test on a single crystal of brass. The work has not been published, and I do not know the crystallographic direction of the axis of the specimen used. Lo-ching Chang (Columbia University, New York)— Observations similar to Figs. 1 and 2 of the paper were obtained by us during the bending and unbending of an orthorhombic Au-Cd alloy.'l This orthorhombic alloy is the product of diffusionless transformation from a single crystal of p Au-Cd alloy (CsC1 structure) containing 47.5 atomic pct Cd on cooling to about 60 "C.62 Referring to the effects of annealing, has the author tried any loilg time high temperature anneal, such as 150 to 200 hr at 40O°C? D. C. Jillson—No. C. Crussard (Ecole des Mines, Paris: France)—I

Jan 1, 1952

G. A. Moore—The tin-fusion method has been a very favorable possibility for many years. The authors apparently have settled the question that delayed the method for a long time by showing that no hydrogen is absorbed in the tin. This, of course, is very important. I want to make a few remarks concerning the absolute accuracy of analysis, which must be the final basis for deciding among the various methods. From the figures in the paper, there seems to be some re-maining slight discrepancy on the actual amount of hydrogen present in various samples which may be presumed essentially identical. (This is of the order of the precision of individual analyses but appears in averaged results.) From the analyst's viewpoint, the tally of hydrogen content can be regarded as occurring in three portions. First is a large portion which comes off easily and automatically during sample storage and later on heating in the apparatus. This is fairly easily analyzed. Second is an item which may be either positive or negative in the tally sheet. In warm or hot evolution, this is a portion which, in practice, can never be re-

Jan 1, 1951

H. G. Haemers (Ghent University, Belgium)—The authors claimed "the results of their work indicate that the metals can be arranged in a sulfation series similar in its application for selective sulfation tot the electromotive series for displacement of metals from solution". The series as stated in decreasing order for tendency of SO3 give up, is the same as that stated by free energy diagrams. Indeed, the degree of stability of a sulfate is measured by the free energy of sulfate formation out of the corresponding metal oxide and SO3. The more negative the value of the free energy (-DG) the greater the stability of the sulfate. As a second consequence this statement results in a relative aptitude for capture of SO3 by each metal oxide when brought in contact with the sulfate of other metals. Let M1 and M1 be the two metals, and — DG1 and — DG2 their free energy values at temperature T. Both sulfates are stable at temperature T if - DG1 < O and — DG2 < O. In case where — DG1 < — DG2 the stability of M1SO4 is greater than that of M2SO4, and when M1O (oxide of

Jan 1, 1958

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

Jan 1, 1960

E. M. Fitchett (Johnstown, Pa.)—The fact stated by the authors that: "In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium," (p. 465, paragraph 3) is most unusual. A similar statement is made in the summary and conclusions: "Germanium alone, within normal operating limits does not cause large efficiency losses." The limits are not defined. These facts are directly contrary to much of the published history on the effect of germanium in zinc electrolysis. A description of the conditions leading to such a successful electrolysis would be of interest to all engaged in the production of electrolytic zinc. It is unfortunate that the authors of this paper did not determine the actual concentration of germanium and cadmium in the solutions which they electrolyzed after a zinc dust purification. This purification will take out a variable amount of these impurities, depending upon the composition of the dust, type of agitation, presence of activating agents, etc. Probably every electrolytic zinc plant in this country has accurate methods, both wet and spectrographic, for determining germanium and cadmium. These specific methods, adopted from the standard analytical literature, are often available to educational institutions for the asking. The headings of Fig. 2 and of the two tables, with their definite concentrations of germanium and cadmium (which are not so definite according to the footnotes) could possibly be somewhat misleading, since the actual amounts of germanium and cadmium present during electrolysis are not known. Even the 1 hr electrolysis time might be too short for a study of this type; 12 or 24 hr tests might be much better. Commercial solutions have been known that gave over 90 pct ampere efficiency during the first hour of electrolysis, but no metal at all after 24 hr.

Jan 1, 1953

E. A. Peretti (University of Notre Dame, Notre Dame, Ind.)—Mr. Deitz and Professor Halpern are to be congratulated on a fine piece of work which adds to our knowledge of precious metal—cyanide-solution reactions. I should like to offer the following comments: The authors state, "the rate plots were always linear, indicating a zero order reaction rate." This appears to conflict with the data of Fig. 6 which clearly show the rate to vary with the NaCN concentration. It seems to me that the rate curves are linear because of the experimental setup. The volume of solution is so large that over a three-hour period the change in NaCN concentration is very small. A rough calculation for the experiments of Table I where the initial NaCN strength was 0.0096 mol per liter show a change of NaCN concentration of about 0.0009 mol per liter at the end of three hours. In short, over the period of time that the experiment was in progress, the NaCN strength was practically constant; hence the rate of dissolution remained practically constant. Eq. 10, as written, specifies that 1 mol of H202 and 2 mol of hydroxyl ion are formed when 2 mol of silver react. Is this true? The effect of H,O2 on the rate was made in solutions having an oxygen pressure of 4.8 atm. Were any tests made in solutions containing hydrogen peroxide, but no oxygen? G. M. Willis (University of Melbourne, Melbourne, Australia)—The authors have shown that, under their experimental conditions of high O2 concentrations, the rate of solution of silver in aqueous cyanide solutions is controlled by diffusion of O2 or CN- to the metal surface. With diffusion control, it is generally not possible to obtain further information about the mechanism of a process.

Jan 1, 1955

R. E. Powers (Mellon Institute of lndustrial Research, University of Pittsburgh, Pittsburgh)—Several of the processing methods at the Josephtown smelter might well be considered by plants producing iron blast furnace sinter. In making blast furnace sinter the objectives are much the same as at Josephtown: To produce a strong yet porous agglomerate which has a size consist in a preferred range. The emphasis however is on production rate rather than on the size or other quality characteristics of the sinter. Therefore the technique is entirely different. Blast furnace sinter plants attempt to make their product in one pass with a minimum recirculating load and without sizing treatment after the sinter leaves the machines. Many plants are beginning to feel that more attention paid to quality characteristics would make the product a more desirable blast furnace material. The pelletizing of very fine material before placing it on the bed is not deliberately done at iron sinter plants, although the installed equipment sometimes gives a simila; action. Such pelletizing seems to be a promising way of accommodating the down-draft sintering Drocess to very fine materials. he recirculating load at Josephtown is extremely high. Two plants&apos; producing blast furnace sinter from raw material of comparable size have a recirculating load of about 100 pct of production. At Josephtown it is notable that the size and the rate of feeding of return fines are under control. This is not the case in most blast furnace sinter plants. The sinter slicer appears to be a worthwhile aid in effecting such control. It is similar in action to rakes and plows used at a number of plants, but it has the advantage that the sinter dislodged is positively removed and not left to the inefficient action of a stationary grizzly screen. Blast furnace size specifications for sinter are not at present so rigid as the Josephtown specifications. If the sizing of blast furnace sinter does become important, then the Josephtown crushing practice, in which a large recirculating load is maintained on the crusher in order that minimum fines be produced, may be of interest. H. K. Najarian (authors&apos; reply)—We note that Mr. Powers appreciates some points that we tried to emphasize in our paper as being of importance in making zinc sinter of good quality and which may well be applied to iron blast furnace sinter. Fig. 2 shows the pelletized nature of the feed going on to a Dwight-Lloyd type sintering machine in our plant. Practically, the entire feed consists of more ,or less rounded particles which permit more uniform air passage through the charge, while the larger particles in the charge roll on to the surface of the grate, which helps to keep the grate openings from being clogged by excessive fines. An agglomerated charge of this character may preferably be made by rolling action while being mixed in a rotating drum and wetted by water sprays to bind the fine particles together and give the charge the desired moisture content. From our observations of several iron ore and blast furnace flue dust sintering operations, we believe that if the fines from the sinter discharged from the machines were to be recirculated and agqlomerated with the new feed, not only sinter of better quality but larger capacity from the machines may be realized.

Jan 1, 1952

By American Institute of Mining Engineers

David J. Mack (University of Wisconsin, Madison, Wise.)—Have the authors considered that the effects reported in their paper are readily explainable on the basis of equilibrium grain boundary segregation rather than ordering? It seems to the writer that all of their experiments and observations correlate well with known behavior associated with equilibrium grain boundary segregation. Although at first glance one would tend to dismiss such a possibility because of the similarity of the gold and copper atoms, their sizes differ by 12.8 pct which is in the range where segregation at grain boundaries would be expected. Then, too, the electrochemical differences between the copper, the Cu3Au, and the gold strongly suggest that a segregation mechanism is involved in the corrosion of the Cu-Au alloys. R. Bakish and W. D. Robertson (authors&apos; reply)—The authors would like to thank Dr. Mack for his consideration of the problem of grain boundary segregation as an explanation of the observed phenomena. We had considered the problem in the following terms: Assuming a pure binary Cu-Au alloy and an ideal solid solution, the surface excess, T2= N25 — N2, of the second component (gold) may be expressed in the following way20 1 —exp (—da/kT) where 8 is the difference in surface tension of copper and gold, and a is the surface area per atom. In the present case, 6 is positive which implies that the component in excess at the boundary is gold. Since the only chemically active component in ferric chloride is copper, it does not appear that the segregation of gold is likely to increase the boundary activity. A small concentration of a third component could profoundly affect the situation. Analysis indicated only spectrographic traces of impurities, all of which are soluble in both copper and gold. Quenching experiments, reported in the paper, also tended to eliminate significant effects attributable to a third component.

Jan 1, 1958

R. W. Balluffi (Atomic Energy Div., Sylvania Electric Products Inc., Bayside, N. Y.)—Since porosity is known to form in the copper side of Cu-Ni couples during diffusion24,25 it is of importance to consider this factor in interpreting the large variations of chemical diffusivity with copper concentration reported for this system. The presence of porosity may affect the measurement of D in two ways: 1—density changes in the couple invalidate the usual solutions of the diffusion equation, and 2—the pores may act as short-circuiting paths when transport through the vapor or along internal surfaces is appreciable or else as open circuits when these effects are small. The error produced by the first effect may be estimated by a graphical analysis. Fig. 8 shows the porosity generated in the copper side of the Kirkendall interface of a pure nickel vs pure copper couple after diffusion for 350 hr at 1040°C in hydrogen. In Fig. 9 the actual diffusion curve which would be obtained by the usual slicing technique is shown as a solid line drawn to the same scale (from the data of da Silva and Mehl"). The amounts of porosity (obtained by lineal analysis) and of nickel are graphically represented by the hatched areas. The standard solutions of the diffusion equation are valid only when all volume elements of unit length and unit cross section contain equal numbers of atoms." It is possible to correct the experimental curve to satisfy this condition by shrinking the couple in the direction of diffusion in such a way as to eliminate the porosity.* The corrected diffusion curve obtained after

Jan 1, 1954

A. Blainey (Ministry of Supply, Atomic Energy Research Establishment. Hnrtoell. England)—With ref- erence to the published work of Hausner et al. on the powder metallurgy of zirconium, it will be of interest to summarize briefly the results of preliminary work we have carried out on this subject at A.E.R.E., Harwell. For the early experiments we used zirconium

Jan 1, 1953

Impact Transition Temperatures of Some Pearlite-Free Mild Steels As Affected by Heat Treatments in the Alpha Range H. P. Tardif (Canadian Armament Research and Development Establishment, Quebec)—Mr. Josefsson is to be congratulated for his study of a most difficult subject and for the theories proposed to explain the re- sults. One point which, however, might not have received proper attention is that of the shape of the stress-strain curve at the yield point of quenched and furnace-cooled specimens and of specimens strain aged

Jan 1, 1956

P. L. Pratt (University of Birmingham, Birmingham, England)—The author has measured the hardening effect of isolated edge and screw dislocation boundaries in a remarkably elegant manner, and he proposes that the detailed structure of the boundary determines its effectiveness as a barrier to slip although "there are still unknown details of the distribution which may be extremely important." On p. 678 the author states "that for a good crystal (one having a yield of about 30 psi) a change in annealing temperature from 300" to 400 °C resulted in a negligible shift in the level of the stress-strain curve." Is this in agreement with the results of the earlier paper by Li, Washburn, and Parker8 in which such a change of temperature produced notable hardening in crystals with a yield of about 30 psi? Or were these earlier crystals, of the same nominal purity, less perfect than those used in this work? The experiment illustrated in Fig. 15, p. 681, shows that the boundary has sharpened after annealing at 400 °C, the temperature at which the hardening effect first becomes apparent. Did the author verify that no sharpening of the boundary occurred at, say, 300 °C where no hardening was found? This would seem to be an important check on the proposed mechanism, especially since zinc of this purity should polygonize at temperatures well below 400 °C within the annealing times used here. There seem to be at least two alternative explanations which could fit these facts: 1—The boundary may sharpen at 300 °C or even lower temperatures but be unable to contribute greatly to the hardening until jogged by thermal vacancies and other impurity atoms after 400 °C anneal. This mechan- ism, discussed in the earlier paper,&apos; is believed to account for the thermal hardening observed by Blank&apos;" in NaCl, as stated elsewhere: and by results from recent experiments which tend to confirm this view. 2—The dislocations in the diffuse boundary may be locked by impurity atoms at 300 °C and thus only sharpen the boundary at 400 °C with the aid of thermal vacancies. In this case it would be difficult to distinguish between the two sources of hardening (sharpening or jogging), using metal of this purity. Jack Washburn (author&apos;s reply)—The author wishes to thank Dr. Pratt for his discussion. In connection with his first comment, it should be pointed out that the temperature of testing in the present series of experiments was —196°C, whereas, in the earlier experiments he referred to,&apos; it was 20°C. Therefore, the yield values should not be directly compared. It is likely that the crystals used in the present work were initially more perfect macroscopically than the large shear specimens used previously. The small size of the test section in the kink specimens made it possible to select regions of the large crystals, from which they were acid-cut, that were free of observable small angle boundaries. The sharpening of a microscopically diffuse boundary such as that in Fig. 15 begins in zinc of this purity well below 300°C. However, it is probably not justified to conclude that because a boundary looks sharp under the microscope it has attained the ideal structure. The author agrees with Dr. Pratt that jogging of dislocation lines is one of the structural features of a small angle boundary that should be important in determining its strengthening effect. More detailed information concerning the changes in boundary structure as a

Jan 1, 1956

J. D. Fast and J. L. Meijering (Philips Research Laboratories, N. V. Philips&apos; Gloeilampenfabrieken, Eindhoven, Netherlands)— After the departure of our friend Dijkstra to the United States, investigations on the effect of alloying elements on the behavior of nitrogen in a iron were continued in Eindhoven. We too found internal friction curves with two separate peaks for iron containing nitrogen in addition to 0.5 atomic pct V or 0.5 atomic pct Mo. Our first publication on these investigations" appeared almost simultaneously with the paper now under discussion. At first sight our experimental results seem to be in harmony with their conclusions, but a closer examination reveals that in the case of the Fe-V-N alloy the abnormal peak is not controlled by one time of relaxation only. Whereas iron containing 0.5 atomic pct Mn or Mo absorbs an amount of nitrogen of about the same magnitude as that absorbed by pure iron under identical conditions, iron containing vanadium absorbs in addition one nitrogen atom for every vanadium atom. This last amount, far exceeding the first amount in the case under consideration, combines chemically with the vanadium and causes no internal friction. The "free" nitrogen in the vanadium alloy gives rise not only to a damping peak corresponding to that in pure iron but— due to the presence of VN particles in the metal—also to the abnormal peak at higher temperatures. The VN particles create interstitial sites around themselves where the free nitrogen atoms are bound much tighter than in the normal interstices. These abnormal interstices, therefore, will capture free nitrogen atoms rapidly, whereupon these give rise to the abnormal damping. The binding energy in the abnormal interstices is not the same for all, and with coarsening of the VN precipitate the distribution of these energies is displaced toward the side of stronger binding. This is deduced from a shift of the summit of the second peak toward higher temperatures (from 80" to 88°C in our experiments) caused by prolonged heating at 950°C. From the intermediate state where they cause the abnormal damping, the nitrogen atoms pass over rather rapidly into the fully precipitated state (iron

Jan 1, 1954

C. M. Bishop (Aircraft Div., A. V. Roe Cnnada Ltd., Toronto)—Reference is made to the coherency hardening of ß due to ß&apos; and also to the hardening of ß due to a coherent precipitation of the a phase. What is meant by the term "ß&apos;?" Would not the coherency hardening of ß during cooling be due to precipitation of a sub-microscopic dispersion of a, as is the case during reheating a ß-quenched alloy? I feel that these two phenomena are essentially the same mechanism, i.e., precipitation of a from unstable or supersaturated ß. From the text, it would appear that Tables III and IV are intended to show the effect of the martensite transformation on the properties of Ti-Mn alloys. Referring to Table 111, the ß-quenched alloys would contain a greater proportion of retained ß than would the equilibrated alloy. Could not the increase in properties be attributed to this, along with possible coherency hardening of the ß? In the same way, the structures referred to in Table IV contain ß from which they could derive their hardness. It would appear to be difficult, if not impossible, to assess the role of the martensite transformation from the data contained in these tables. F. C. Holden, H. R. Ogden, and R. I. Jaffee (authors&apos; reply)—In reply to the first question raised by Mr. Bishop, the term "ß"&apos; designates an apparent retained-p structure which is harder than it is after the most rapid cooling from the ß field. It is thought to be the result of a coherent precipitation of a. The mechanism by which hardening takes place is undoubtedly the same as that involved in the early stages of aging of a re-tained-p structure, and we are in agreement with Mr. Bishop on this point. The term "ß&apos;" to designate the anomalously hard retained-ß structure was agreed upon at a symposium in 1953." The authors do not agree that the quantity of retained ß and/or ß&apos; in the ß-quenched specimens of Table III is necessarily greater than that of the 600°C equilibrated specimens. The ß-quenched specimen has a structure which appears to be completely a&apos; formed by the martensite reaction. It is recognized that there could be some retained ß (or ß&apos;) between the a plates if the M, temperature is below room temperature. This is unlikely for the 3.4 pct Mn alloy where the M, is known to be at about 640°C. Therefore, the increase in strength cannot be attributed to the presence of a greater quantity of coherency-hardened ß, but, rather, the increase in strength must be attributed to the transformation products formed, e.g., a&apos; (martensiti-cally formed a). Concerning the data in Table IV, we agree that it is difficult to estimate the role of the martensite reaction, since the 6.4 pct Mn alloy was retained ß in the quenched condition.

Jan 1, 1955

G. D. Kneip, Jr., and J. 0. Betterton, Jr. (Union Carbide & Carbon Corp., Oak Ridge, Tenn.)—The authors have contributed to the theory of zone melting by considering the effects of the solidification of the final zone on the distribution curves for the finite length bar. However, they do not consider in sufficient detail the restrictions imposed by the particular metals involved. Eq. 4 has the analytical solution which is equivalent to Pfann&apos;s&apos; equation for normal solidification of the final zone. For distribution coefficients less than one, it is apparent from this form of the equation that, as the solidification approaches completion, the concentration attains extremely large values which are inconsistent with the density of physical materials. The necessary restrictions then are that the solute concentration cannot exceed the density of the alloy, or more frequently, the solubility limit in the solid phase. Secondly, the distribution coefficient cannot be constant from 0 to 100 pet solute unless the liquidus and solidus coincide over this whole region. It would thus be more correct to impose limits on the solubility such as would be indicated by a typical eutectic diagram. Furthermore, in this case the assumption that the distribution coefficient remains constant is more likely to be realized. Eq. 4 should then be replaced by the following C,,(x) =k/L-x [ ?11 3 C11 (x)Ddx - ?11 4 Cn(x)dx= k[Cn (L-l)/k] [ L-x/l]x-1 L-l = x = L-l [kCenterlie/Cn (L-l)]1/k-1 The typical shape for the distribution curve in the final zone is indicated schematically in Fig. 12 for the simple eutectic case. The solidification proceeds according to Pfann&apos;s&apos; expression until the concentration reaches the maximum solubility in the solid phasc. At this point, the concentration changes abruptly to the eutectic composition and remains at this value for the duration of the solidification. The width of the flat region, and the back reflection of this effect into the concentration curve on subsequent passes, depends upon the ratio of the eutectic concentration to the original concentration, upon the distribution coefficient, and upon the number of passes. Similar effects on the concentration curves in the first zone length would be expected in many systems for which the distribution coefficient is greater than one, and where the maximum solubility is not too much larger than the original concentration. The discussers agree with the authors that the assumption that the liquid is uniform in concentration should be considered with caution. Kneip and Better-ton&apos; have shown, however, that in floating zone refining of zirconium, using induction heating, the distribution of iron agrees with theory which assumes a uniform liquid composition. Hence, in this case, the experimentally realized distribution coefficient agrees with the present phase diagram within the experimental uncertainty. L. Burris, Jr., C. H. Stockman, and I. G. Dillon (authors&apos; reply)—The authors are happy to have received the comments of G. D. Kneip, Jr., and J. 0. Betterton, Jr., which provide additional insight into the zone refining process. It is true that the equations developed are inapplicable if the solute solubility in the solid phase is exceeded. However, this restriction on the use of the equations was clearly stated in the paper. A closer approach to

Jan 1, 1957