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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' 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

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

Jan 1, 1958

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,' is believed to account for the thermal hardening observed by Blank'" 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'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,' 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

C. M. Bishop (Aircraft Div., A. V. Roe Cnnada Ltd., Toronto)—Reference is made to the coherency hardening of ß due to ß' and also to the hardening of ß due to a coherent precipitation of the a phase. What is meant by the term "ß'?" 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' reply)—In reply to the first question raised by Mr. Bishop, the term "ß"' 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'" 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' 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' formed by the martensite reaction. It is recognized that there could be some retained ß (or ß') 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' (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

Jan 1, 1957

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's' 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's' 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' 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' 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

Jan 1, 1955

DISCUSSION, M. Cohen presiding A. H. Geisler and D. L. Martin (GeneTal Electric Research Laboratory, Schenectady, N. Y.)—We were rather interested to note the author's conclusion that the cubic to tetragonal transformation may be of the second order, for we have been able to show that the order-disorder transformation in an analogous alloy system is a first-order transformation with a discon-

Jan 1, 1952

P. Herasymenko (New York University, New York) —The authors' experiments on equilibria between water vapor and liquid synthetic slags represent a valuable contribution to our knowledge of the nature of liquid slags. They can be regarded as a proof of ionic splitting of water molecules dissolved in slags. The assumption that water dissolved in slag was com- pletely ionized was made in my report on hydrogen equilibria in steelmaking as early as 194010. In that paper, the first systematic data were given on the content of ionized hydrogen in acid and basic open-hearth slags. The paper probably escaped the notice of the authors, although they mention the articles published later by other investigators who reported erratic and

Jan 1, 1958

E. T. Turkdogan (British Iron & Steel Research Assoc., London, England)—I would like to suggest a different method for the treatment of the authors' data on the Si-0 equilibrium in liquid iron. Because the activity coefficient of silicon dissolved in iron is influenced by the concentration of silicon as well as that of oxygen, the equilibrium constant K2 of reaction 2 becomes a function of metal composition, and, as shown in Fig. 1, a plot of log KP1 at 1600°C against the weight percent of silicon gives a smooth curve. A similar curve is obtained when log Kzl is plotted against the oxygen content of iron. Before

Jan 1, 1955

E. A. Loria (Product Metallurgical Engineer, Crucible Steel Co. of America, Pittsburgh)—In this interesting paper, our introductory work was quoted. We would like to call attention to our sequel paper on the experimental determination of oxygen in cupola-melted cast iron,20 which was not mentioned. Vacuum-fusion oxygen values (as well as hydrogen and nitrogen) were reported for nine heats of cast iron melted in the Battelle 10-in. cupola under normal operating practice and under oxidizing conditions. The oxygen analyses ranged from 12 to 68 pprn compared to the author's computed range of 10 to 80 ppm. The average amount of oxygen found in our irons was about 20 pprn and changes in the silicon content of the iron from 1.32 to 2.35 pct had no consistent effect on the oxygen content of the iron. The gas determination specimens were poured in split steel molds that produced a clean pin, 3/8 in. diam and 2 in. long. Because freezing was almost instantaneous, the pins were entirely white iron (nongraphitic). In the early stages of the investigation, the pins were transferred to a mercury-filled trap system immediately after pouring. This was done to collect gas evolved between pouring and analysis. However, it was found that during storage for 4 weeks gas evolution was negligible. Because the vacuum-fusion analysis was usually completed within 4 days of pouring, pins from later heats were not stored in the mercury-trap system. We found some evidence that cast iron picks up oxygen during long storage, because of rusting. Earlier work by the British Cast Iron Research Association has shown that cast irons may be stored for a long time without significant change in their oxygen content. The practical significance of this study (and our own) would be in the improvement of cast-iron quality. Has the author investigated this aspect and reached any conclusions on the effect of oxygen on the mechanical properties of cast iron? The second phase of our study was to determine the properties of the test bars poured simultaneously with the gas analysis specimens. We realize that there may be complicating factors attendant in this procedure.21 Results from many test specimens measuring chill depth, transverse flexure and deflection strength, spiral fluidity, and sensitivity to hardness of gray irons ranging from 12 to 68 pprn oxygen showed that the lowering of transverse strength was the only significant undesirable effect of high oxygen content. A statistical study of the chill test results21 showed that the iron containing 22 to 46 pprn oxygen had forced chill depths that were 2/32 in. below the expected value from their composition, and irons containing less than 16 ppm oxygen had forced chill depths averaging 1/32 in. greater than the expected chill depth. Higher oxygen contents, within the range of 12 to 68 pprn did not increase forced chill depth. With the wedge tests, there was a good linear relationship between carbon equivalent of the irons and their chill depth. The results indicated that oxygen contents below 50 ppm in the iron did not affect chill depth. With 50 to 70 ppm oxygen in the iron, oxygen appeared to have a slight graphitizing tendency. These results are in disagreement with the common belief in gray iron foundries that "oxidized irons" produce high chill depths. It would be appreciated if the author would comment on this subject. Gustaf Ostberg (author's reply)—In Fig. 1 the legend of line I should read 2 pct C, 1 pct Si. The author wishes to thank Mr. Loria for calling attention to his later work, which was published after the present paper was concluded. The range of oxygen contents quoted seems to agree well with the author's values. The lack of response to variations in silicon content is probably due to the fact that the oxygen content in most cases was below the saturation level. The absence of temperature dependence, even in the case of saturation, is understandable if the difficulty in formation and escape of the deoxidation products is taken into account.

Jan 1, 1960

John Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—After looking over the authors' shoulders for several years and after many discussions on the interesting diagrams of the types shown, it is a pleasure to see a formal paper published on this subject. There can be no doubt of the practical usefulness of the concepts shown. Inclusion formation in steel is such a highly complex matter that any system for understanding the subject is bound to be welcomed by those who must work with steels and who see in their day-to-day experience the good and evil effects of inclusions. A feature of the work with which the discusser has been concerned, and which he would now like to attempt to explain, is the relation between the schematic diagrams which the authors use and the phase diagrams for related systems. Obviously, the authors' diagrams are in no sense complete phase diagrams. However, there is a relation between this type of diagram and the true phase diagram, and the understand- ing of this relation ought to help in understanding the general picture which the authors are presenting. Consider the authors' Fig. 4, which shows the liqui-dus relations in the Fe-Mn-S-0 system. To show the complete relations between temperature and composition in these four ternary systems would require four triangular prisms, the vertical axes of which would represent temperature. The four triangles of Fig. 4 represent basal projections of certain lines from the four prismatic phase diagrams. Readers of the paper are all more or less acquainted with this type of projection and its usefulness and limitations are generally understood. In order to concentrate on the interesting parts and to minimize the less interesting features, the composition scale may be shifted to de-emphasize regions containing gaseous sulphur and oxygen. Such a diagram is shown in Fig. 16, which is a distorted version of the authors' Fig. 4. Here the oxide of iron is wiistite, denoted by W, and it is to be noted that between W and MnO lies the entire MnO-FeO "binary" system. Similarly, between MnS and FeS lies another binary whose

Jan 1, 1956

R. W. Guard (General Electric Co., Schenectady)— The method of fractional replication discussed by the author has proven very valuable to us in applied research connected with alloy and process development where many of the same experimental difficulties exist. Several of our experiences may be of assistance to those who want to apply the method in these fields. Contrary to the author's observation that interactions are rarely significant, we have found in a number of cases that first order interactions exist which are significant and metallurgically important. Because of this difference there are two further precautions which should be taken in order to minimize the difficulties from this point. First, in evaluating the importance of

Jan 1, 1957

E. Hill, South Norwalk, Conn. (communication to the Secretary*) :—The phenomenon described by Dr. Ledoux, involving an apparently abnormal high temperature in the air-cylinders of compressors, has not been, so far as I know, discussed in technical literature. The common formula for the adiabatic compression of dry air does not account for heat suficient to flash ordinarily decent cylinder-oils, nor do the text-books include in their theoretical statements any quantitative consideration of the effect of leaks in the ideal machines which they contemplate. This lack I have endeavored to supply by preparing, in the form of a circular, for the use of the customers and correspondents of the Norwalk Iron-Works, a brief mathematical

Jan 1, 1904

Adolph Greiner, Seraing, Belgium:—I have nothing special to add to Professor Hubert's paper except to say that there are some little things that it would be well to have corrected when the paper comes to be published. In dealing with the thermal efficiency of the engine, you will find that the 29.84 per cent. was a very high one. Professor Hubert has forgotten those engines built under the Cockerill type, but he has referred to them in Appendix 11. At our works at Cockerill we have built 63 engines, giving 63,000 h.p., and the other companies who have received licenses have built 113 engines, making 103,000 h.p., and aggregating 176 engines and 166,000 h.p. Eight years ago I had the pleasure of giving to the Institute the results obtained up to that time. Since then a good many engines have been constructed. In 1898 I thought a blast-furnace producing 100 tons of pig iron would allow 3,000 h.p. Professor Witz and Professor Hubert show that with the same production of pig the new engines take 3,800 h.p. out of the gas. At present at Cockerill we make 700 to 800 tons of pig iron per day, and we hope to have 26,000 h.p. in a few years. At present we have only half of that in gas-engines, but we hope to have in five or six years all the gas out of these furnaces to the number of 25,000 or 26,000 h.p. Tom WEstGarth, Middlesbrough, England :—My contribution is not a paper in the ordinary sense of the word, because I am sure you will agree with me that what I have written is only supplementary to the other two papers. The notes are schedules of the larger-size gas-engines built by British engine-makers, of 500 h.p. and upwards. If you look at the schedules you will find that in England gas-engines have become quite ordinary motors for a good many purposes. It was at first thought that gas-engines were troublesome, and ill-

Jan 1, 1907

R. V. NorHis, Wilkes-Barre, Pa. (communication to the Secretary*) : The electric-haulage plant of the Short Mountain Colliery of the Lykens Valley Coal Co., mentioned by Messrs. Stoek and Harris as the earliest underground electric plant in the United States (and, I believe, the second in the world), was started July 23, 1887. The plant, designed by W. M. Schlessinger, consists of two motor-cars, each weighing about 5 tons and equipped with a 32-h.p. Union Electric Go. motor. The original general construction of the motor-cars is shown by Mr. Stoek; but they were rebuilt, the same year, with some important improvements in design; and, except for strengthening the frames and replacing the original pig-iron weights by a casting, they have not been greatly changed since that time. The generating-plant consists of two Union Electric Co. dynamos of 65-h.p. each, driven by an old 18- by 48-in. plain slide-valve engine; the ordinary voltage is 450 and the amperage varies from 40 to 200; the average indicated h.p. of the engine is about 75, with a steam-consumption of about 75 lb. per i.h.p. per hour; and as the cost of steam at this colliery is 8.11 cents per 1,000 lb.,the steam-cost per day is about $4.56.

Jan 1, 1904

R. W. Raymond, New Pork, N. Y.:—I think Mr. Bache has put his finger on the chief source of the danger of dust-, or gas-and-dust, explosions in collieries. 1 mean the persistent determination of the miners' unions to increase their weekly wages by the excessive use of explosives. This would not be feasible if coal-miners were paid by the day; but this form of payment is, for many reasons, not economically practicable; and the universal practice is to pay for the winning of coal according to the quantity produced. If the miner, by using a large amount of powder, can throw down a large amount of coal without corresponding labor on his own part in undercutting and drilling, he will receive more money for less work, provided he is paid for everything—merchantable coal, worth-less dust, slate, and " bone "—resulting from such a method. My attention was called to this matter many years ago by an admirable report of Prof. W. B. Potter, a past- President of the Institute, on the conditions obtaining in this respect in the Illinois coal-field. It was made very clear in that report that considerations of danger to workmen or loyalty to employers could not be relied upon to prevent miners from employing this perilous and wasteful method of increasing their own immediate receipts. So far as I know, only three remedies have been attempted, namely: the enforcement of discipline as to the methods of mining; the refusal to pay for dust, etc., produced by the miners'methods; and restriction upon the use of explosives, effected by requiring the miner to purchase them from the employer, at a price so high as to make it unprofitable for him to use them in excess. All of these attempted remedies have encountered the bitter opposition of the miners' unions. The enforcement of discipline has become almost impossible, if discipline be (as it should be) understood to involve punishment for the violation of rules when no disaster has followed. I

Jan 1, 1910

William Kent, New York, N. Y.:—The Institute may congratulate itself on the opportunity of reading the splendid address of President Brunton. It is an admirable summary of the progress that has been made in the mining and metallurgical arts in recent years. The paper rightly gives the chief credit for this progress to the aid which has been rendered to these arts by the advances in mechanics, chemistry, and electricity. It is notable that most of the headings in Mr. Brunton's address refer to the work of the mechanical engineer, the electrical engineer, and the chemist, rather than to that of the specialist in mining-operations. It seems that the most successful mining engineer of the present day is the one who makes the most intelligent application of the inventions and designs of engineers and others who are not directly engaged in mining. A tabulation of the headings of the address, grouped as below, shows this most clearly. Work of the Mechanical Engineer—Rock-drills, hoisting-machinery, tramming, pumping, ventilation, dredging, Sampling, concentration, briquetting, fume-recovery. Work of the Electrical Engineer—Electric machinery for hoisting, pumping, tramming, lighting and signaling, electric transmission, electric smelting. Work of the Chemist and Metallurgist—Explosives, chlorina-tion, cyanidation, roasting, lead-smelting, and copper-smelting. Work of the Geologist—Economic geology. Work of the Mining Engineer—Mine-mapping, surface-mining, timbering, tunneling; and planning and supervision of the work in general. The mining engineer of the present day, who is in responsible charge of a large plant, finds his chief work not in doing those things he was trained to do as a specialist, but in making use of the knowledge of geologists, chemists, and electrical and

Jan 1, 1910

DR. PeRsifor Frazer, Philadelphia, Pa. (communication to the Secretary):* Mr. Campbell's very interesting contribution, after complimentary mention, finally decides against the acceptance of the classification proposed by me in a paper bearing the same title and read at the Wilkes-Barre meeting, May, 1877.2 That paper was written primarily for the Second Geological

Jan 1, 1906