By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton
T. E. Leontis (The Dow Chemical Co., Midland, Mich.)—This paper is of particular interest to me because of my own work with F. N. Rhines on the oxidation of magnesium and magnesium alloys a few years ago. The authors are to be complimented on their development of an accurate and reproducible technique for measuring ignition temperatures and on their comprehensive study of the many variables that affect the ignition temperature of magnesium. It is indeed gratifying to see that they have obtained a good correlation between ignition temperatures and the oxidation rates reported by us. The correlation is valid not only with composition within one alloy system but also between alloy systems; that is, alloying elements which effect the greatest increase in oxidation rate also produce the greatest decrease in ignition temperature. There are a few points upon which I would like to comment. In attempting to correlate ignition-temperature data, one must be sure that the same definition of this quantity is used by all investigators. It does not appear to me that such is the case in the authors' comparison of their data with the theoretically calculated values of Eyring and Zwolinski. The equation derived by these investigators defines the ignition temperature, To, as the temperature at the gadoxide interface, whereas the present authors use the metal temperature as the criterion for ignition. The contradiction in the effect of oxide-scale thickness on ignition temperature between the predictions of the Eyring-Zwolinski equation and the observations reported in this paper indicate that some variable has not been taken into consideration. Could that be the geometry and size of the specimen? There is a marked difference in the type of specimen used in this investigation and that used in our work which formed the basis of Eyring and Zwol-inski's theoretical treatment. Another factor which plays an important role in ignition is the vapor pressure or the rate of vaporization. Combustion can safely be assumed to take place in the vapor phase by the reaction between vaporized magnesium and oxygen. Thus, a more accurate theoretical analysis may be made on the basis of the rate of vaporization which may be the controlling rate of the process. The effect of a large number of alloying elements on the ignition temperature has been reported in this paper, but beryllium was not included. Practical experience dictates that beryllium markedly decreases the burning tendency of magnesium. I was wondering if the authors plan to study the effect of beryllium in their future work. The authors predict that concentrations of sulphur dioxide in the furnace atmosphere greater than 5.8 pct would be expected to increase the ignition temperature to values still higher than those they measured. I would like to mention that large concentrations of sulphur dioxide markedly increase the rate of combustion of magnesium once ignition has started. Although it has been shown in the paper that the ignition temperature of magnesium in oxygen increases with increasing sulphur dioxide content up to about 1 to 2 pct, in practice relatively low-melting commercial cast alloys (AZ63A and AZ92A) are being continuously heat treated at temperatures just below the melting point in air containing 0.5 to 0.75 pct SO*. In regard to the change in color of the oxide scale observed on magnesium and magnesium alloys just prior to ignition, I would like to mention that in our work alloying elements were found to color the usually white magnesium oxide even though ignition did not occur. For example, the oxide formed on Mg-A1 alloys was gray, increasing in intensity with aluminum content in the alloy. Finally, I might suggest that the authors indicate their source of the value of 0.8 g per cc for the density of MgO as it is formed on magnesium upon oxidation at elevated temperatures. W. M. Fassell, Jr. (authors' reply)—The comments by Dr. Leontis are very excellent ones and I will attempt to answer them in order. First, the problem of ignition of magnesium is a rather difficult one since many factors are involved. Concerning the comparison of the To in the Eyring-Zwolinski equation, eq 4, with the experimentally determined values, it will be noted that the calculated and experimental values of the ignition temperature in Table I are not self-consistent. In the case of the 1.78 pct A1-Mg alloy the calculated value is 49°C below the experimental value; for the 3.81 pct A1-Mg alloy, 122°C below the experimental value; for Mg with 5x10-' cm film, 19°C above the experimental value; for Mg with 2x10-I cm film, 28 °C below the experimental value. Thus, if it were merely a matter of difference of location of temperature measurement the calculated ignition temperature would always be below the experimental value, the difference being due to the thermal gradient through the oxide film. The possibility of a thermal gradient in the magnesium metal must be considered. From Carslaw and Jaeger,'Y t can be shown that the maximum temperature gradient that could exist between the oxide-metal interface and the center of the sample is of the order of O.Ol°C. The geometry and size of the specimen could certainly have some effect on the ignition temperature. The equation for ignition that has been proposed in reference 14 is of the following type containing terms to account for this and other factors: M dT AHv(T) =Cp--------------\-J(.T—TB) + ZAHl-M A dx where AH is the heat of reaction, v(T) is the velocity of the reaction at temperature, Cp is the heat capacity of sample, M is the mass of sample, A is the area of sample, t is time, J is the total coefficient of heat transfer outward from the reaction zone, TR is the temperature of the bath or furnace, and AH,, is the heat associated with any phase change involved. Prior to the instant of ignition, the vapor pressure of magnesium is of no special significance. After ignition, neither eq 4 nor the above equation is applicable. The actual combination of magnesium cannot safely be assumed to take place in the vapor phase. While experimental data is lacking to support a hypothesis that ignition does or does not occur in the vapor phase, some observation on the pressure ignition experiments may be of interest. At high oxygen pressures, once ignition has occurred, the reaction of magnesium with oxygen approaches near explosive violence, the entire sample being consumed in probably less than 1 sec. At atmospheric pressure it usually requires 15 to 20 sec. Thus it appears that the oxygen concentration becomes the rate determining factor. Further, if burning magnesium is observed through darkened glass (Lincoln Super-visibility Shade No. 12) the magnesium sample is very much hotter than the "smoke" and the outline of the sample is retained perfectly. No "flame" is visible above the metal. No work was done on Mg-Be alloys. We do, however, intend to study this problem in the near future.
REPUBLIC STEEL CORP. and Armco Steel Corp. have joined in a $160,000,000 project for the production of iron ore from Taconite in the Lake Superior mining region. The two companies announced acquisition in equal shares of 100 pct ownership of the stock of Reserve Mining Co., which controls a vast deposit of magnetic Taconite iron ore on the eastern end of the Mesabi range in Minnesota. Through Reserve Mining the two companies will build a plant for manufacturing high grade ore from Taconite near Beaver Bay on the north shore of Lake Superior. The first announcement calls for about a $60,000,000 plant which will be built as soon as plans are completed and will have an annual capacity of about 2,500,000 tons of iron ore pellets. Longer range development plans call for future expansion of the plant to provide an annual capacity of 10,000,000 tons. This will amount to an additional investment of
Demand for eastern magnetite in 1948 necessitated practically all eastern magnetite industries to operate on a six-day week, with the result that over 11,000,000 long tons of crude ore were mined, and the shipping products amounted to approximately 5,000,. 000 long tons. Reports indicate that operating on a six-day week and doing maintenance work on the seventh day was satisfactory and resulted in excellent continuity of operation. In the Port Henry district, Republic Steel Corp. once again set new all-time records for the production of crude ore and total shipping product; 1,868,000 long tons of crude ore were mined, 945,000 from the Old Bed mine, 408,500 from the Harmony mine, and 514,500 from the Fisher Hill mine. Of the 969,000 long tons of shipping products, 663,800 long tons were sinter, 181,000 lump ore, and 115,200 con¬centrates.
G. A. Burr, Parral, Chihuahua, Mexico (communication to the Secretaryt): I regret that Mr. Norris did not give more attention to the hoisting of water in inclined shafts or slopes: the only slope mentioned being Hickory Ridge Slope, No. 4, of the Union Coal Co. The surface arrangement, illustrated in Fig. 12 of his paper, if not unpractical, is at least unscientific and cumbersome. It is my opinion that the back- and sideguides shown in Fig. 12 are not only unnecessary where rails are used as a track, but are unsafe, excepting in the case of a very firm hanging-wall, or roof, and sides of vein-matter, having absolutely no tendency, either to settle from the back, or to squeeze from the sides, an effect which would inevitably force the guides out of alignment. The accompanying illustration, Fig. 1, shows what I consider a better method of hoisting water than that described by Mr. Norris. This method is based on the general practice in metalliferous mines of the West, where skips are used in slopes; and, while it is not original with me, I have frequently used it with very satisfactory results for dumping both ore and water.
OUR colleges and universities have met many difficulties during the past year. From a period of small enrollments and depleted faculties, the educational institutions have passed quickly to a period of the largest enrollments in their history with inadequate facilities and staffs. The results of the shortsighted policy of the Selective Service system which drained the technical schools and universities of many of the students who were potential teachers are now being felt. The movement of faculty members into positions in industry during the war years has resulted in many of them forsaking permanently the educational field for the higher salaried positions they now occupy. Competition is keen between the educational institutions, and between the institutions and industry, for technically trained men. Dean Holbrook's statement in last year's annual review that he thought it would take three or four years to restore our engineering departments to their former level in quality of instructors is even more convincing today. Somehow, the institutions must not only reach their former level in quality of instruction but they must also increase the quantity of their staffs to meet the demands of the ex-service men and the high school graduates for engineering education. The enrollments in the mineral industry fields of mining, metallurgical, geological, petroleum, and ceramic engineering, although greatly increased, are not expanding as much as in the more widely known fields of electrical, mechanical, aeronautical, and civil engineering. In fact, many educators are tremendously worried about the segregation of so many young men in a relatively few fields while the needs of others will remain unanswered.
Institute of Metals Division - Ignition Temperatures of Magnesium and Magnesium Alloys - Discussion