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Jan 1, 1904

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 Tomlinson makes reference to an unpublished work which, he claims, shows that titanium dioxide behaves the same as silica in regard to conductivity.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

Jan 1, 1951

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

DISCUSSION, A. Y. Bethune presiding M. E. Wadsworth and W. M. Fassell (University of Utah, Salt Lake City)—The authors of this paper should be complimented on the experimental techniques they have employed to investigate the rate of solution of galena in sodium hydroxide solution. Studies of this type are important not only as a practical means of leaching normally non-leachable substances, but also to determine the mechanism of solution at the solid-aqueous solution interface. There is some question, however, as to the conclusions which have been drawn by these authors concerning their proposed mechanism. Unfortunately, the contribution of OH- was not definitely established in their work, and concentrations less than 0.5 N NaOH evidently were not investigated. The pressure data at 123°C and 0.5 N NaOH were used to determine pressure dependency and the subsequent model proposed was taken as correct on the basis of the three points presented in Fig. 5 of the paper. In developing the

Jan 1, 1954

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

DISCUSSION, T. B. King and H. H. Kellogg, Chairmen Philipp Gross (Fulmer Research Institute Ltd., Stoke Poges, England)—As pointed out by the author, any better agreement between experimental and calculated

Jan 1, 1956

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

Lester Guttman (General Electric Research Lab-boratory)—Seybolt has measured the thermodynamic activity of silicon in dilute solution in a iron. The anomaly which appears at 800 °C in the approximate range 1 to 6 wt pct Si is most naturally attributed, as Seybolt has done, to the existence of a region of

Jan 1, 1960

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

R. L. Fleischer (Department of Metallurgy, Massachusetts Institute of Technology)— The authors have presented valuable observations of oehavior of aluminum at intermediate and high temperatures. I should like to consider their interpretation of the appearance of cross slip plane traces in sample B-3 as partly due to "bending of the crystal due to grip constraint." Because bending moments might be set

Jan 1, 1960

Jan 1, 1958