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By J. Chipman, G. G. Hatch

One of the important functions of the iron blast furnace is the desulphur-ization of pig iron before it enters the steelmaking furnaces. However, the increasing concentrations of sulphur in the metallurgical coke, source of approximately 90 pct of the sulphur present in the blast furnace charge, and demands for higher rates of production within recent years have increased the need for greater desulphurization within the iron blast furnace. Furnace operators are beginning to look for desulphurizing agents other than blast furnace slag to accomplish the desired degree of desulphurization. A considerable amount of work has been done on desulphurization outside the furnace with soda ash, calcium carbide and various synthetic slags. Whether the desulphurization of pig iron is accomplished wholly inside the furnace or partly inside and the remainder outside, will be determined by the economics involved. Regardless of which is the case, it is believed that it is necessary to have a better understanding of the physical chemistry of desulphurization by blast furnace slags. To this end, it is the object of the present investigation to attempt what is believed to be the first equilibrium study of the distribution of sulphur between liquid pig iron and a wide range of blast furnace slag compositions. Review of Literature There is a considerable amount of information in the literature concerning the desulphurizing power of iron blast furnace slags, the solubility of various sulphides in the slags, and the effect on desulphurization of temperature, of elements dissolved in the liquid iron, and of viscosity. However, there is nothing to indicate that the equilibrium distribution of sulphur between liquid iron saturated with carbon and iron blast furnace slags has been studied experimentally. Wentrupl has made probably the most detailed study of the desulphurization of pig iron to date. He considered that there are three distinct aspects involved, namely: 1. Desulphurization within the blast furnace (by lime and manganese). 2. Subsequent desulphurization by manganese. 3. The effect of subsidiary reactions on the desulphurization by manganese. The experimental work carried out by Wentrup was devoted mainly to obtaining a better understanding of how desulphurization by manganese was accomplished in the mixer and the ladle. Particular attention was given to the part played by carbon, silicon, and phosphorus associated with manganese in the iron, and the effect of temperature on desulphurization. The experimental results indicated that desulphurization by manganese is purely a process of crystallization of manganese sulphide. The addition of silicon to iron melts containing 3.5 pct carbon and less than 0.5 pct manganese had no noticeable effect on desulphurization, but with 1-2 pct manganese the silicon additions improved the desulphurization. Additions of phosphorus also resulted in improved desulphurizati011 by manganese, but the effect was not as marked as in the case of silicon. It was also found that desulphurization by manganese was further improved by lowering the temperature. In order to explain desulphurization inside the blast furnace, Wentrup considered the system iron, sulphur, calcium, oxygen, manganese. (silicon). The distribution of sulphur between the metal and slag was represented by the following equation: (SS) _ (S)Fe + (S)Ca + (S)Mn .... [S] = [s] [1] The parentheses and the brackets represent the equilibrium concentrations in weight per cent of the slag and metal constituents, respectively. Since FeS D (FeS) _ (FeS) (S)Fe LfeS - [FeS] [S] [2] (CaO) + S e (FeO) + (S)Ca _ (FeO)(S)Ca. (S)Ca _ (CaO) Kl = (CaO)[S] [S] ~K1(FeO) [3] Mn + S D (S)Mn (S)Mn (S)Mn K' = [MnpT "1ST = *lIMnJ !4) Substitution of Eq 2, 3, and 4 into Eq 1 resulted in if = L- + *> (Sol + K^ (S) [51 Eq 5 was used to calcu1;lte -f^j and [S] at 1480°C for slags containing 30-50 pct lime, 0.1-2.5 pct iron oxide, 0-26 pct silica, 2 pct sulphur and iron analyzing 1.5 pct manganese. The value for LFaB at 1480°C was found to be equal to 4.5, based on the experimental work of Bardenheuer and Geller.2 The results of the calculations are shown in Table 1. Although the slags are hypothetical and do not represent the range of compositions found in ordinary blast furnace practice, the calculations indicate that lime is effective in controlling desulphurization only if the iron oxide and silica contents of the slag are kept low. Schenck3 did not claim K1 to be a true equilibrium constant, but an empirical value which varied with the silica content of the slag.

Jan 1, 1950

By W. Rosotoker

Using an expression for the free energy of a homogeneous phase as a function of composition, a relationship is derived which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. Comparisons between observed and calculated phase boundaries in the systems Fe-Ni, Fe-Mn, Fe-W, Ti-Mo, and Ti-Cb are presented. IT is the purpose of this paper to illustrate how the general free energy equations for two phases in equilibrium may be used to derive an expression which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. The free energy per gram atom of a disordered solid solution may, for many purposes, be represented by the equation:' F = ½NZ [C-V,, + (1-C) VbB + 2C (l-C)V] + K(T) +RT[C-lnC+ (l-C)ln(l-C) ] [1] where N is Avogadro's number; Z, the coordination number; C, the concentration of the solute element in atomic percent; the subscripts refer to concentrations at phase mixture boundaries; VAA, VBB, and V,, are the bond energies between like and unlike adjacent atoms, respectively, at the interatomic spacing characteristic of the phase. The bond energies are usually assumed to be independent of small changes in the lattice parameter occasioned by solute additions and variations in temperature; V = VAB ---------------—— ; K(T) is the sum of the heat con- tent and heat entropy; R, the molar gas constant; and T, the temperature in degrees Kelvin. The free energy of a homogeneous phase is there- fore the sum of an internal energy, a specific heat, and a configurational entropy term, respectively. The compositions of two phases in equilibrium at a given temperature are governed by the minimum total free energy principle. Graphically, this is represented by the points of tangency of the tangent common to the free energy vs. concentration curves of the two phases. Analytically, this may be expressed as: ( df) = (df) [2] dc dc Expanding both sides using eq 1, the following equation is obtained after convenient readjustment of the terms: RT In[(ca)(1-c)]-½N (Vaa-Vbb)(Za-Zb) +NV [Za(l-2Ca)-Z,(l-2C,)] [3] The following assumptions have been made at this point: 1—The specific heats of the two phases are independent of composition variations within the range under consideration. Accordingly, the K(T) terms disappear on differentiation. 2— (Vaa)o = (VAA); (VBB). = (VBB); Va = V, Theyjustification for these assumptions can lie only in the successful application of the resultant equation. It may be noted that Zener2 has used assumption 1 in the calculation of the boundaries limiting the (a+j3) phase mixture in the Cu-Zn system.

Jan 1, 1952

Executive Committee, Board of Directors Augustus B Kinzel, Chairman, J L Glllson, Vice-Chairman, A W Thornton, Howard C Pyle, Grover J Holt Finance Committee, Board of Directors Andrew Fletcher, Chairman, J S Vanick, Gall F Moulton Investments Gail F Moulton, '60, Chairman, Henry Krumb, '59, J Loveloy, '61, C R Dodson, ex off as Treasurer, Andrew Fletcher, ex off as Chairman, Finance Com¬mittee Endowment Andrew Fletcher, Chairman, N G Alford, H DeWitt Smith, W J Coulter, J V N Dorr, R B Gilmore, J B Haffner, O H Johnson, D H McLaughlin, J R McMillan, L F Reinartz, C E Weed, Wilfred Sykes, J R Suman Honorary Memberships H DeWitt Smith, '59, Chairman, C E Reistle, Jr, '59, Grover J Holt, '59, L F Reinartz, '59, M L Haider, '60, D H McLaughlin, '61, John M Lovejoy, '62, Augustus B Kinzel, ex off as President

Jan 1, 1958

By Colin M. Sargent

THE electron diffraction pattern as seen in the electron microscope represents an approximately plane section of the reciprocal lattice. Identifying the zone axis of a diffraction pattern is often laborious for a crystal of low symmetry, especially if several crystal orientations are present. A program has been written in FORTRAN II (Version 2) for the IBM 1620 which will assist in plotting out reciprocal lattice sections. The calculation is performed by choosing a zone axis [uvw] and determining the d spacings and angle between the planes (Ow - v) and (wO - u). (This procedure is varied slightly for zone axes with Miller indices equal to zero.) Cartesian coordinates for the reciprocal lattice points are then calculated for these planes and for (ww— [u + v]). Any reciprocal lattice points within the parallelogram formed by the origin and these three points are then computed. The input and output are best described by use of an example (Monoclinic ZrO2) used in the author's work. Input consists of two cards: 1) The crystal parameters: a, b, c, a, 8, y, e.g., 5.1477, 5.2030, 5.3156, 90.000, 99.380, 90.000. 2) Three numbers, D, E, F, e.g., 5, 3, 3.0710-the first is the limit of the sum (u + v + w) considered; the second limits the absolute value of u, v, and w to (E- 1), e.g., 2, so that zones (221) would be the highest order considered in this example; the third, F, is the required constant, yL. Output is in the format shown in Table I. The reciprocal lattice sections may then be plotted on standard graph paper and compared with the unknown diffraction pattern. (Note that no attempt has been made to deal with systematically absent reflections.) A card deck for the program is available from Colin M. Sargent, ARZ, W-PAFB, Dayton, Ohio, 45433.

Jan 1, 1969

By W. C. Peters, M. W. Pullen, C. A. Bays

During the past three and a half years considerable improvement in the techniques of solution extraction of salt has been made by the use of wells which are cross-connected by hydraulic fracture at the base of the salt. Fracture is initiated by the application of hydraulic pressure. Underreaming and perforating techniques are used to control initiation. The fracture is then extended by continuous pumping until a pressure communication is obtained. Pressure communication is followed by washing-through to obtain a low-pressure connection. Well construction using non-shrinking cements that will bond with the salt and with associated strata is essential to the process. The connecting procedure described permits solution to attack the salt deposit from its base upward, thereby permitting greater recovery, fewer well repairs, better saturation of brine, and overall economy of development and operation. The fracture method of cross-connection requires special pumping of the fluid and is limited by present experience to initial well spacings up to about 1200 feet. The method has been used in bedded salts and is applicable for wells in salt domes. Since spring of 1956, new developnents in salt extraction wells have followed procedures substantially different from those in prior use. Although multiple well systems, connected either by the natural consequence of the solution process or by undercutting under protective pads, have been used previously, the past three and a half years have brought about new designs and new operation procedures based on cross-connection of the wells using hydraulic fracture. To date these techniques have been applied largely in the bedded salt deposits of Michigan, Ontario, Ohio, West Virginia, and New York. To the writers' knowledge they have not been used in salt dome wells. The methods have not yet been in use for a sufficient period to permit any statistical comparison with the older methods. It is evident from experience to date that the methods result in higher recoveries, lower capital and operating costs, better saturation of produced brine, reduced well maintenance and repair, and in considerably fewer production units to insure

Jan 1, 1961

First Session BRASS Wednesday, A.M., Nov. 29 Co-Chairmen: CARTER S. COLE, Staff Engineer, A.S.T.M. E. A. ANDERSON, Chief of Metals Section, Research Div., New Jersey Zinc Co. (of Pa.) Second Session BRASS Wednesday, P.M., Nov. 29 Co-Chairmen: D. K. CRAMPTON, Director of Research, Chase Brass and Copper Co., Inc. A. W. TRACY, Metallurgist, The American Brass Co. Dinner and Technical Session Wednesday Evening, Nov. 29 Toastmaster: N. L. MOCHEL, Manager Metallurgical Engineering, Westinghouse Electric Corp. Talk on "How Do Things Look Today and For the Future" RALPH KELLY, President, Baldwin Locomotive Works Technical Paper on Stress-Corrosion Cracking E. H. Dix, JR., Assistant Director of Research and Chief Metallurgist, Aluminum Company of America Third Session BRASS Thursday, A.M., Nov. 30 Co-Chairmen: W. B. PRICE, Director of Research, Scovill Manufacturing Co. A. L. JAMIESON, Associate Metallurgist, Frankford Arsenal First Session LIGHT METALS Thursday, P.M., Nov. 30 Co-Chairmen: L. L. WYMAN, Metallurgist, General Electric Co. M. A. HUNTER, Professor of Metallurgical Engineering and Head, Dept. of Metallurgical Engineering, Rensselaer Polytechnic Institute Second Session LIGHT METALS Thursday Evening, Nov. 30 Co-Chairmen: R. T. WOOD, Chief Metallurgist, American Magnesium Corp. J. D. HANAWALT, Director, Metallurgical Dept., Dow Chemical Co. First Session STEEL Friday A.M., Dec. I Co-Chairmen: H. S. RAWDON, Chief, Division of Metallurgy, National Bureau of Standards A. L. FEILD, Director of Research, Rustless Iron and Steel Corp. First Session MISCELLANEOUS METALS Friday P.M., Dec. I Co-Chairmen: E. A. ANDERSON, Chief of Metals Section, Research Div., New Jersey Zinc Co. (of Pa.) CARTER S. COLE, Staff Engineer, A.S.T.M.

Jan 1, 1945

ONE DAY IN the mid-1880s, in a suburb 0f Pittsburgh, Pennsylvania, there dismounted from a train the two foremost leaders of the day in the coal and steel industries-Andrew Carnegie and H. C. Frick. Their attention was drawn to a well-loaded car of coke, which their experienced eyes recognized as a superior product. "I'll bet you that coke is from the H. C. Frick Coke Company," Mr. Frick challenged. "I'll bet it was shipped by my company." In a spirit of fun Mr. Carnegie accepted the wager. Mr. Frick lost the bet: the coke had come from M0rewood, one of three sites being operated under the direction of a young entrepreneur, Erskine Ramsay. If Mr. Frick's confidence was somewhat dented by this occurrence, the responsibility was his own. He himself had opened the way for Erskine Ramsay to become the youngest of mine superintendents; and he had dispersed all dissension regarding his choice with the words : "I'm not interested in his years, I'm interested in his record. He makes more coke in an oven than any other superintendent. And I'll take 'em out 0f the cradle if they can make coke... Suppose he is only twenty years old? ... The d --- kid is a genius, I tell you." Erskine Ramsay was to follow in the tradition of Carnegie and Frick. Not only was he ambitious and a worker his background had prepared him for it. Coal mining was in the Ramsay blood. His father, Robert Ramsay, of whom the son once stated that he had no superior as coal mining and mechanical engineer in this country, once accounted in these words for the phenomenal accomplishments which had attached to the name "It does no harm to belong to a family of mining engineers who are just as good as any in America-if it is myself that says it." Anyone acquainted with Robert Ramsay's character realized that he was not given to overstatement. And the above-mentioned Mr. Carnegie encountered young Ramsay again, a few years later in his career, and wrote of him to young Erskine's father, that he was "going to be a credit `tae us a' " (a quotation from Robert Burns.) Nor have Mr. Ramsay's achievements been identified exclusively with the industrial field in which he early asserted himself. He has been an inventor whose techniques in mining engineering have received international recognition. As an investor of foresight, he has benefitted others immeasurably, as well as himself, being an influential factor in the upbuilding of several communities in his chosen and well-loved adopted home state of Alabama since 1887. He is a philanthropist whose benefactions have run into millions, the chief beneficiaries being educational and charitable institutions. Amidst his accomplishments the lighter side of life has not been neglected and he is known for his hospitality, his

Jan 1, 1953

By J. Stuart Warner

The reaction COSO4(c)?CoO(c) + So3(g)was investigated from 950° to 1170OK by two different methods. The sulfate was decomposed in a previously evacuated space and Pso3 calculated from the measured total pressure on the assumption that Pso2 = 2P02. The sulfate was also decomposed under conditions of controlled oxygen pressure. The difference in the results obtained by these experimental techniques is attributed to the effects of thermal diffusion. The standard free energy change for the reaction is given by ?F° = 66,292 + 17.273T log T — 102.57 T (±300 cal/mole). It was found by DTA and X-ray diffraction studies that CoS04 undergoes a transformation at 617°± 4°C. THE metal sulfates may decompose directly to the oxide or pass through one or more intermediate basic sulfates. Provided the oxidation state of the cation does not change in the course of the reaction, the decompositions may be described in general as follows: One of the major objectives of this work was to determine the validity of Eq. [3] as much of the existing sulfate data has been calculated from decomposition pressures by Eq. [5]. The type of apparatus generally used for these measurements consists of a reaction vessel at high temperature which communicates with a manometer at room temperature. A temperature gradient is thus imposed on the gas phase causing thermal diffusion which brings about a partial separation of the different gaseous species present in an initially uniform mixture. The basic theory and experimental facts associated with this phenomenon are summarized elsewhere1 and it will suffice to state here that the heavier gaseous species diffuses down the temperature gradient. Since thermal diffusion destroys the homogeneity of the gas phase, it is not necessarily true that Pso2 = 2Po2 in any particular volume element of the gas phase even though there are twice as many molecules of SO, as of 0, in the gas phase considered as a whole. Under these conditions, the decomposing sulfate gives off SO, which dissociates to SO, and 0, and all three species are distributed throughout the system by thermal diffusion. However, the sulfate will continue to dissociate until the equilibrium value of PSo3 is established on the hot zone. Thermal diffusion may distribute SO2 and O2 throughout the gas phase in any way so long as Eq. [2b] is satisfied in the hot zone; i.e. Pso2(Po2)1/2=K3pso3. When a steady state is reached, we can characterize Pso2 in that

Jan 1, 1962

By A. M. Gaudin

Jan 1, 1962

Institute of Metals Iron and Steel Mineral Industry Industrial Minerals Year Division Petroleum Division Division Coal Division Education Division Division 1918 W. M. CORSE ' 1919 " 1920 W. H. BASSETT 1921 1922 W. B. PRICE RALPH ARNOLD 1923 E. DEGOLYER 1924 G. K. ELLIOTT 1925 " F. JULIUS FOHS 1921; PAUL D. DIERICA " 1927 JOHN M, LOVEJOY 1928 S. SKOWRONSKI A. W. AMIBROSE RALPH Fl. SWEETSER 1929 " J. B. UMPLEBY G. B. WATERHOUSE 1930 ZAY JEFFRIES C. V. MILLIKAN \V. J. MACKENZIE HOWARD N. EAVENSON 1931 SAM TOUR C. E. BEECHER F. AT. BECRET 1932 C. H. MATHEWSON EARL OLIVER F. N. SPELLER THOMAS G. FEAR , C. H. FULTON 1933 T. S. FULLER W. E. WRATHER JOHN JOHNSTON ELI T. CONNER 1934 .J. L. CIIIRISTIE H. D. WILDE, .JR. L. F. REINARTZ T. T. READ 1935 W. M. PEIRCE HARRY H. POWER A. B. KINZEL JOHN T. RYAN SAMUEL H, DOLBEAR 1936 E.H. DIX,JR. HALLAN, N. MARSH C. E. WILLIAMS EUGENE McAULIFFE WILLIAM B; PLANK' OLIVER BOWIES 1937 A. J. PHILLIPS AL ALBERTSON FRANCIS B. FOLEY J. B. Moscow " CHESTER A.. FULTON 1938 R. F. MEHL G. B. CORLESS J. T. MACKENZIE PAUL WEIR FRANCIS A.THOALSON J. R. THOENEN 1939 R. H. LEACH W. I-1. G E I S J. HUNTER NEAD C. A. GIBBONS " AT. M. LEIGHTON 1940 C. A1. WISE T. V. MOORE F. T. SISCO C. E. LAWALL W. R. CHEDSEY W. M. WEIGEL 1941 D: K. CRAJIPTON E. A. STEPHENSON C. H. HERTY, JR. JULIAN E. TOBEY " . PAUL AT. TYLER 1942 CARL E. SWARTZ HARRY P. STOLZ E. C. SMITH NEWELL G. ALFORD A. F. GREAVES-WALKER B. L. MILLER 1943 CYRIL STANLEY SMITH C. A. WARNER HERBERT W. GRAHAM CADWALLADER EVANS, JR. " HOWARD 1. SMITH 1944 ARTHUR PHILLIPS W. S.-MORRIS WILLIAM A. HAVEN A. W. GAUGER A. C. CALLEN C. H. BEHRE, JR

Jan 1, 1944

By Craig R. Barrett, Oleg D. Sherby

The creep characteristics of four pure metals with widely Varying stacking-fault energies (silver, copper, nickel, and aluminum) were evaluated above 0.5Tm. Creep tests were performed under conditions of constant atomic diffusivity and constant stress over the elaslic modulus. The sleady-state creep rate, Es, was found to he a funclion of the THE most common empirical representation of the steady-state creep rate, Es, at high temperatures and intermediate stresses is of the form where a is the applied stress, E is an elastic constant, A and n are constants (n is typically stacking-fault energ, y, such that Es is proportional to y3,5. In addition, it was uncovered that the primary creep strain and the strain to fracture increased with increasing y, and that the ratio of initial to steady-state creep rate decreased with increasing y. about 5), Q is the activation energy for creep (usually equal to that for self-diffusion), and kT has its usual meaning. sherbyl and McLean and ale' have used this expression to correlate creep data for a number of pure metals. An interesting aspect of Eq. [I] is the absence of any dependence on the stacking-fault energy. While most creep data seem to obey the stress and temperature dependence predicted by Eq. [I], when data for several metals are put on a master plot they do not fall on a common line but form a band. The width of this band corresponds to a variation in Es of 102 to l03. sherbyl attempted to explain this band by assuming that a grain-size effect was present which led to the observed variation. On the other hand, Felt-

Jan 1, 1965

J. L. CHRISTIE, Chairman T. S. FULLER, Past-chairman W. M. PEIRCE, Vice-chairman W. A. SCHEUCH, Vice-chairman E. M. WISE, Secretary International Nickel Co., Bayonne, N. J. W. M. CORSE, Treasurer Executive Committee H. A. BEDWORTH G. O. HIERS D. K. CRAMPTON R. H. LEACH E. H. DIX, JR. R. F. MEHL J. A. GANN J. WALTER SCOTT' JEROME STRAUSS Finance Committee T. S. FULLER, Chairman W. M. CORSE H. S. RAWDON C. H. MATHEWSON SAM TOUR

Jan 1, 1934

By J. Richter, D. Schulze

J. Richter and D. Schulze (Deutschen Akademie der Wissenschafte zu Berlin)—Introduction. In a recent paper R. G. Garlick and H. B. Probst reported on experimental results of investigations of room-temperature slip in zone-melted tungsten single crystals.17 In the paper it was pointed out that slip lines could be detected with an optical microscope only after about 10 pet plastic strain of the crystal. In our investigations we could observe slip lines in tungsten single crystals of defined orientations already with an elongation of 0.02 to 0.03 pet.18"9 Experimental Technique and Results. The tungsten single crystals were produced from 4 to 5 mm sintered rods* as starting material by electron- beam zone melting. With single-zone-pass melting a speed of 0.5 mm per min was used, while three-pass melting could be handled at a speed of 3 mm per min. Crystal axis orientations were located in the shaded area of the stereographic triangle, see Fig. 6. Orientation 1 is located at about 18 deg and orientation 2 at about 5 deg on the great circle from [011] to [ill]. This corresponds approximately to the orientations P and M referred to by Garlick and Probst. Our single crystals had a length of about 70 mm and were profiled solely by electrolytic means, leaving grip ends at both ends of the crystals. Between the latter, a cylindrical crystal of 45 to 50 mm length and about 2.4 mm diam was obtained. The crystals were deformed at room temperature in a commercial tensile-testing machine to obtain a strain of 0.02 to 5 pet. The average strain rate e = eP/t for all tensile tests amounted to approximately 10 -6 to 10-5 per sec, with ep representing plastic strain and t the duration of applied stress. In Fig. 7 a crystal is shown elongated by 0.03 pet. The picture was obtained by means of an optical microscope. Figs. 8 and 9 give electron-microscopic pictures of slip lines of crystals elongated by 0.07 and 1.1 pet, respectively. For crystals with the orientation 1, see Fig. 6, only the two main slip systems (101)[111] and (110)[111] were found. With the crystals of group 2 the two main slip systems are again evident, with

Jan 1, 1965

By G. V. Smith, C. O. Tarr, R. F. Miller

Metallurgists have long recognized that the Fe3C type of carbide is not a stable phase in steel and that, given sufficient time, it will decompose with formation of graphite, at least at temperatures below about 205o°F.l This slow graphitization has never been of much concern to users of hypoeutectoid steels, for in such steels it occurs only during prolonged exposure at elevated temperature. In I935, Kinzel and Moore2 reported complete graphitization of the carbide of a 0. I5 per cent carbon steel that had been in service for about 26,000 hr. at a temperature of about IIOO° to 12oo°F. In discussing this paper, both Mathews and Sauveur reported graphitization of slightly hypereutectoid steels. In an extensive investigation of graphitization of high-purity iron-carbon alloys, Wells1 produced graphite at 7oo°C. (I29o°F.) in an alloy containing as little as 0.13 per cent carbon, and showed that graphite may precipitate either directly from austenite or from decomposition of Fe3C, also that the rate of graphitization tends to increase with increase of temperature, at least up to a certain point, and with the presence of graphite nuclei. Jenkins, Mellor and Jenkinson,3 studying the structural changes in carbon steels ranging from 0.17 to 1.14 per cent carbon during stress-rupture tests at elevated temperature, observed graphite in an aluminum-killed 0.40 per cent carbon steel after fracture in 4340 hr. under a stress of 17,900 lb. per sq. in. at 840°F. and in many of the steels after stress-rupture test at 12oo°F. Unstressed samples of 0.60, 0.86 and I.I4 per cent carbon steels graphitized almost completely in 360 hr. at I200°F., while samples of 0.90 and 1.10 per cent carbon steels were somewhat graphitized, and steels containing 0.24, 0.40 and 0.57 per cent carbon showed no sign of graphite. Their results indicate that graphite precipitates the more readily the higher the carbon content, though this tendency is influenced to some extent by deoxidation practice, and that graphitization is accelerated by plastic deformation. In a recent study of the graphitization of 0.4 and 0.6 per cent carbon steel strip, made by M. A. Hughes,4 it was found that at I2oo°F. graphite appeared after 72 hr. in aluminum-killed but not in silicon-killed steel, and that the rate of graphitization was increased by slow cooling from I6oo°F. and by cold-working prior to annealing. In creep tests of normalized 0.15 per cent carbon steel killed with 2.5 Ib. of aluminum per ton, at the U. S. Steel Corporation laboratory at Kearny, spheroidization and some graphitization were found after 3000 hr. at Iooo°F. under a stress as low as 1500 lb. per sq. inch. .

Jan 1, 1944

By C. O. Tarr, G. V. Smith, R. F. Miller

Metallurgists have long recognized that the Fe3C type of carbide is not a stable phase in steel and that, given sufficient time, it will decompose with formation of graphite, at least at temperatures below about 205o°F.l This slow graphitization has never been of much concern to users of hypoeutectoid steels, for in such steels it occurs only during prolonged exposure at elevated temperature. In I935, Kinzel and Moore2 reported complete graphitization of the carbide of a 0. I5 per cent carbon steel that had been in service for about 26,000 hr. at a temperature of about IIOO° to 12oo°F. In discussing this paper, both Mathews and Sauveur reported graphitization of slightly hypereutectoid steels. In an extensive investigation of graphitization of high-purity iron-carbon alloys, Wells1 produced graphite at 7oo°C. (I29o°F.) in an alloy containing as little as 0.13 per cent carbon, and showed that graphite may precipitate either directly from austenite or from decomposition of Fe3C, also that the rate of graphitization tends to increase with increase of temperature, at least up to a certain point, and with the presence of graphite nuclei. Jenkins, Mellor and Jenkinson,3 studying the structural changes in carbon steels ranging from 0.17 to 1.14 per cent carbon during stress-rupture tests at elevated temperature, observed graphite in an aluminum-killed 0.40 per cent carbon steel after fracture in 4340 hr. under a stress of 17,900 lb. per sq. in. at 840°F. and in many of the steels after stress-rupture test at 12oo°F. Unstressed samples of 0.60, 0.86 and I.I4 per cent carbon steels graphitized almost completely in 360 hr. at I200°F., while samples of 0.90 and 1.10 per cent carbon steels were somewhat graphitized, and steels containing 0.24, 0.40 and 0.57 per cent carbon showed no sign of graphite. Their results indicate that graphite precipitates the more readily the higher the carbon content, though this tendency is influenced to some extent by deoxidation practice, and that graphitization is accelerated by plastic deformation. In a recent study of the graphitization of 0.4 and 0.6 per cent carbon steel strip, made by M. A. Hughes,4 it was found that at I2oo°F. graphite appeared after 72 hr. in aluminum-killed but not in silicon-killed steel, and that the rate of graphitization was increased by slow cooling from I6oo°F. and by cold-working prior to annealing. In creep tests of normalized 0.15 per cent carbon steel killed with 2.5 Ib. of aluminum per ton, at the U. S. Steel Corporation laboratory at Kearny, spheroidization and some graphitization were found after 3000 hr. at Iooo°F. under a stress as low as 1500 lb. per sq. inch. .

Jan 1, 1944

By W. O. Philbrook, K. M. Goldman, G. Derge

T. Rosenqvist—The most interesting point in this paper is the observed transfer of iron into the slag in the initial stage of the desulphurization process, after which the iron again is reduced to the metallic state. The authors interpret this observation as showing that the sulphur enters the slag as an iron-sulphur compound which subsequently is decomposed by the slag. The present writer has previously suggested the following equation for the desulphurization process: S + O2- ? S2- + O For equilibrium in the blast furnace the oxygen potential is defined by equilibrium with graphite and CO of 1 atm pressure: C + O ? CO [2] During the desulphurization process the reactions proceed in the direction of the arrows. If one assumes eq 2 to be significantly slower than eq 1, the transfer of sulphur into the slag, in accordance with eq 1, will build up a local oxygen potential at the metal-slag interface very much higher than that corresponding to the value defined by eq 2. This is possible because the equilibrium oxygen potential in eq 1 is high as long as the sulphur content in the slag is low. This oxygen potential will again be able to oxidize some iron: Fe + O ? Fe2+ + O2- and an increase in the iron content of the slag will be observed. Adding up eqs 1 and 3 one obtains: S + Fe ? S2- + Fe2+ The net effect is thus in harmony with the experimental observation but is obtained without assuming any close ties between the sulphur and iron atoms during the process. Furthermore, it follows from eqs 1 and 2 that when the sulphur content in the slag increases, and equilibrium with C and CO is finally approached, the local oxygen potential at the metal-slag interface will decrease, and the iron in the slag will be reduced back into its metallic state. C. E. Sims-—The data and conclusions presented in this paper are thoroughly convincing in establishing the mechanism of sulphur transfer from iron to slag as in a blast furnace. The evolution of gaseous CO in step 3 of the reactions given on p. 1112 makes the process virtually irreversible. Assuming that the process is similar in slag-metal systems other than in the blast furnace, it is readily seen why free CaO and re-ducing conditions so greatly favor desulphurization. On the other hand, the very effective desulphurization obtained in oxidizing slags when strongly basic, must be attributed to the relatively high stability of CaS as compared to FeS. The ease and simplicity with which the reactions of classic chemistry agree with the experimental data and explain the mechanism is noteworthy. The concept of molecules of FeS, soluble in both phases (metallic iron is not soluble in the slag), migrating from the iron to the slag and there reacting with CaO, which is soluble only in the slag phase, is clear and uncomplicated. This is likewise true for step 3. Those who would deny the existence of molecules or molecular-type combinations in liquid iron, must strain to provide a mechanism so lucid. In the absence of molecules, the Fe and S exhibit a remarkable collusion. L. S. Darken—The investigation and interpretation of rate phenomena in the range of steelmaking temperatures is a difficult task. Most of the laboratory investigations of steelmaking reactions have been concerned with equilibrium. Having determined the equilibrium, our attention naturally focuses next on the mechanism and rate of approach to equilibrium. The authors seem to have contributed substantially to our understanding of these factors for the case of sulphur transfer. I should like to ask the authors whether they consider that the sulphur transfer reaction is diffusion controlled as many high-temperature reactions seem to be. If so, it would seem reasonable to suppose that the slow diffusion step of the process is the transfer across a pseudo-static layer or film similar to that considered in heat flow problems. As the diffusivity and fluidity are smaller for the slag than for the metal, it may tentatively be assumed that the sulphur gradient exists in a thin layer in the slag adjacent to the slag-metal interface and that the metal and the main mass of slag are each maintained uniform by convection. On this basis the amount of sulphur transferred across unit area per unit time is D p (?S%)/100 ?1, where D is the diffusivity, p the density, (?S%) the difference in percent sulphur on the two sides of the layer, and ?l is the layer thickness. At the beginning of the experiment the main body of the slag and hence one side of the layer contains no sulphur; therefore (?S%) may be replaced by (S%), the sulphur content of the slag at the slag-metal interface, which in turn is equal to L[S%] where [S%] is the sulphur content of the metal and L is the distribution coefficient. The rate of transfer thus becomes DpL[S%]/100 ?l, which the authors designate K[S%]. Equating these two quantities and setting D = 10-6 cm2 per sec, p = 3 g per cm3, L = 40, and K = lo-+ g cm-2 sec-1, it is found that ?l, the film thickness, is about 0.01 cm—a value of the order of magnitude of that found in heat transfer problems in liquids. The uncertainty of the numerical values used leaves much to be desired, but at least it can be said that this calculation tends to support the proposed model involving diffusion through a film. Although this does not seem to affect the general argument, I should like to call attention to the fact that the diffusivity3 of sulphur in hot metal is found (on conversion of units) to be about 10-4 cm2 per sec rather than 104 cm2 per sec as stated by the authors. The three equations written by the authors to express the steps in the overall process of sulphur transfer may alternatively be written ionically as only two Fe + S = Fe++ + S-- Fe++ + O-- + C (graphite or metal) = CO (gas) + Fe where the underscore is used to designate the metallic phase; ionic species are slag constituents. After the authors have so neatly demonstrated that iron and sulphur transfer together (at least initially), this fact seems almost self evident; from eq 4 it is seen that if sulphur acquires a negative charge during transfer

Jan 1, 1951

By E. C. Smith

THE CHAIRMAN.-Mr. Earle Smith- has kindly offered to make some remarks in connection with segregation in the product, Mr. Smith: E. C. SMITH,* Cleveland, Ohio-I will start this off by a story of the code days of the American Iron and Steel Institute. In those days, Republic did not have a big strip mill, and the question came up of the check analysis of rimmed steel. I suggested that they let me be the chairman of the Committee on Accumulating the Information on the Variation of the Composition of the Ingots of Rimmed Steel. Somebody wanted to know why I wanted to be the chairman. I said, "We don't make any of the big ingots of rimmed steel, and no matter who makes them they are so bad that you don't dare publish the information. So if I collect it and hide it you can't charge me with having done anything that really disrupted the commercial situation. So, everybody furnished me with a rather complete story as to the horrible variations in big rimmed ingots. I took it out to my house and put it away, and it is still there. Now, segregation in the big ingot is no longer an "-academic-matter-as far as II am concerned. ¬I am in a situation like that of the German who was told in 1936 about the coming war. He said: "Until it is your throat that is going to be cut, you don't pay any attention to what is happening to the other man." That is the way with the problem that we have in front of us. Recently I have been told that the comptroller was questioning the payment for certain articles of stamped steel that had been made from rimmed steel, because upon check analysis of the rimmed steel it had been determined that these stamped articles were not within the compositions that were included in the specification, and therefore he as the comptroller had no alternative. It was not meeting the specification; therefore, no payment. So I would say to all of you: You can very seriously consider this matter of segregation now and on into the future on the basis of the fact that it is actually going to cost your companies, which are making these products, money unless there is some new idea about the infallibility of quantitative chemists who analyze some of these products or lawyers who read specifications. I don't know which man is going to be the major factor in the future. If the National Bureau of Standards could in some way show the specification writers the variation between good chemists analyzing for what they expect to be umpire results, the writers would certainly realize that some of the specifications to which we have calmly signed our names as being O.K. are well, as one man said to me, they might be filled by the devil, and they, certainly could be filled by the Lord, but they could not be filled by mankind. I would like to inject two or three things into a segregation study which I want you to think about, because I would be a little surprised if there is very much discussion of them. In the first place, we generally make steel in the United States in the basic open hearth, and I do not think there has been nearly enough consideration given to segregation within the bath before it moves into the ladle. I am sure that any of the people who handled the 9400 series of the NE series when it contained the 0.60 per cent silicon have more respect than they had previously for the segregation that is within the ladle; that is, before the metal reaches the ingot mold, the frozen ingots and the segregation in them. Another point to which I think we ought to give serious consideration is the segregation of iron oxide in the ingot-iron type of material, where the distinction between that and the steel segregation is that it is actually segregating iron oxide. Normally we are segregating some form of carbon or sulphur, or something like. that, with the stamping steel industry now coming down into the ranges of chemistry, where the segregation of iron oxide will be just

Jan 1, 1944

By W. R. McMillan, E. A. Gulbransen, K. F. Andrew

Annealed and electrolytically polished pure iron was oxidized between 650° and 850°C at oxygen pressures of 0.1 to 2 microns Hg. Electron optical studies showed that oxidation occurs discontinuously over the surface and orients crystallographically with the substructure of the metal grains. IN previous papers', " the authors described the formation of oxide films on high purity iron at norrnal pressures and at temperatures below 300°C. Electron optical studies showed that the oxide film consisted of many individual oxide crystallites having nearly random orientation on each metal grain. The size of the oxide crystallites depended upon the temperature and upon the extent of oxidation. In these studies the crystallite size varied from 250 to 1800Å. Recently, Bardolle and Benard3 studied the crystal habit of the oxide crystallites formed on Armco iron between 650" and 850°C in what might be defined as a "poor vacuum" atmosphere in which the pressure could be varied between 10-1 to 10-3 mm of Hg. Their results showed that, at 850°C and a vacuum of l0-2 to 10-3 mm of Hg, a few well oriented nuclei of oxide were formed on the metal grains. At pressures between l0-1 to 10-2 mm of Hg, many oriented nuclei of oxide were formed. At 750°C the metal surface was bright although an oxide was present. Unfortunately, the extent of oxidation, the oxygen pressure, and the influence of carbon in the metal were not determined, and it was, therefore, impossible to give a theoretical interpretation to the very beautiful light micrographs. Bardolle and Benard used the light microscope to determine the crystal habit of the oxide and X-ray diffraction to determine the orientation relationships. It was believed that the use of controlled amounts of oxidation at high temperature is an important method for the study of the initial stages of oxidation of metals at high temperatures. This paper presents the first results of an electron optical study of this problem for iron. Since the electron microscope and electron-diffraction methods using stripped oxide films and surface replicas yielded finer details of the crystal habit and structure of oxide film, these methods were used in this study. Two types of iron having different carbon contents were used: Puron and Armco* iron. A com- parison of the results for these materials made possible a study of the influence of the surface oxide-carbon reaction on the initial stages of oxidation. Before discussing the experimental results, the thermodynamic equilibria of 1—the oxidation reaction, 2—the surface oxide-carbon reaction, and 3—the solubility of oxygen in iron, will be considered. In addition, it is important to consider the kinetic-theory predictions on the rate of collision of oxygen with the iron surface. Thermodynamic and Kinetic-Theory Calculations Only one type of reaction is usually considered in the oxidation of iron at normal pressures at high temperatures: Fe(a) + 1/2O2(g) = FeO(s) 3Fe(a) + 2O2(g) = Fe3O4(s) 2Fe(a) +3/2O2(g) = a-Fe2O3(s). [11 However, two other reactions may occur: FeO(s) + C (solid solution in Fe) + Fe(a) + CO(g) [2] and Fe(a) + O2(g) e Fe(a) (solid solution of 0,). [ 3 ] In addition, iron will react with the higher oxide at certain temperatures to form FeO. For a complete interpretation of the oxidation of iron at low pres-

Jan 1, 1955

In 1962, minerals beneficiation showed definite signs of coming out of the doldrums into which it has drifted after the uranium boom. Demand by steelmakers for high-grade iron pellets has created the need for concentrating plants to upgrade specular hematite by spiral concentration or flotation and magnetites by magnetic means and flotation. According to a paper given at the AMC annual meeting by C. S. Arms of Pickands Mather, "the shipment of pellets, started in the mid-1950's, has increased to 17.6 million tons in 1961 from North American operations. Many plants already underway will raise this production to about 42 million tons by 1965. This will be a very sizeable percentage of the total iron ore production contemplated by that date." Iron ore concentration methods are gradually raising the assay of pellets into the 65 to 69% Fe range and lowering silica to the 4 to 7% range. Quebec Cartier's Lac Jeannine concentrator went into operation in late 1961 and all grinding units were running by 1962. The Iron Ore Co. of Canada's new Carol Lake plant was started in mid-1962.

Jan 2, 1963

By M. Deighton, R. N. Parkins

The metals Cd, ,Wg-, Sn, TI, Zn, and Zr reach a peak hardness after a criticfir1 deformation by rolling- and then soften with fwther rolling-, thereby exhibiting wovk softening. Optical metallography on Cd, Mg, and Zn shows that work softening is accompanied by a change in grain size occurring during deformation. The creep of zinc from -1l° to +60°C at stresses in the range of 7.9 to 17.3 kg per sq mm is given by € = e0 -t- Bt + Kt +at6. The third and second rate constcints are related by the equation a = K~ K6 and their stress and temperature dependence can be represented by the equations K = A, . exp - (u, - Bu)/kT. A model based upon the stress activated glide of sub-boundaries is proposed which qualitatively accounts for the metallog-raphic observations. Expressions, which are in reasonable quantitative agreement with the ex-pe~inzental observations, are derived for the creep of zinc. THE term "work softening" has been used previously by Polakowski1 and by Cottrell and stokes2 to describe phenomena where further strain of a deformed material leads to a decrease in flow stress. In both cases, however, the conditions were changed for the second straining. Here, the term "work softening" is intended to refer to a decrease in flow stress after continued straining in the same direction at the same temperature: work softening is the antithesis of "work hardening". Work softening of zinc was reported by chadwick3 and in discussion of that paper Jenkins4 indicated that cadmium also work softens. More recently work softening has been reported5 in two magnesium alloys, -99.5 pct Mg. Chadwick found that the hardness, 0.2 pct Proof Stress and the UTS of electrolytic zinc all increased with progressive cold reductions up to 30 pct and then progressively decreased with further rolling. Gay and Kelly6 used a back-reflection X-ray technique to study the effect of cold rolling zinc and found that although deformations greater than 2 to 5 pct reduction in thickness produced some recrystallized grains, deformations greater than 40 pct caused com-plete spontaneous recrystallization. At deformations greater than 60 pct the material was found to consist solely of recrystallized grains, -20 pm diam, the size of which decreased with increasing reduction and was much less than the initial grain size of the annealed material (-300 pm diam). Similar results were also reported for cadmium, tin, and lead.6 Gay, Hirsch, and Kelly' suggest that these experiments indicate recrys-tallization takes place when the dislocation density exceeds a certain value. However, no measurements of MATERIALS AND EXPERIMENTAL PROCEDURE The purity of the metals used in this work is indicated by the following figures: Zn (99.99); Cd (99.94); Mg (99.95); T1 (99.99). The zirconium was iodide crys tal bar with a probable purity of about 98 pct. The metals were obtained in the form of 0.25 in. thick strip or 0.425 in. diam rod by various fabrication methods and then annealed to ensure complete re-crystallization. Hardness-deformation curves were obtained at room temperature by rolling 4 in. thick strip under conditions which left a surface adequate for diamond pyramid hardness tests immediately after rolling. The hardness was taken as the niean of five impressions made using a 5 kg load and the time elapsing between rolling and making the last impression never exceeded 5 min. The zinc specimens for creep testing were from 3 by 3 by 4 in. cast slabs which were rolled to 0.10 in. thickness starting at 350°C and finishing cold. The resulting strip was cut into pieces 1 in. wide and annealed in batches. With suitable choices of annealing temperature between 100" arid 400°C five different grain sizes varying from 4.54 x 10' to 3.03 x l05 grains per sq cm (530 to 20 um diam) were obtained. Creep tests were done in compression using a sub-press, based on a design after Ford,8 in which the strip is compressed between dies 0.100 in. wide under conditions of plane strain. Since there is no lateral spread of the material, the area of contact between the dies and strip remains constant throughout the test and the application of a constant load, using the load maintaining device of a hydraulic testing machine, resulted in a constant stress. Covering the dies with strips of P.T.F.E. reduced frictional effects to a minimum. The creep strain was obtained by measuring the travel of the crosshead of the testing machine to a sensitivity of 0.1 pct reduction in thickness. The complete subpress assembly was contained in a steel box and for tests above the ambient this was filled with liquid paraffin and heated electrically. Temperatures below the ambient were obtained with a cooling mixture of acetone and solid carbon dioxide in the box. The liquids were stirred and the temperature of the specimen, which was controlled to ±0.5"C dur-ing a test, was measured by a thermocouple placed near the dies. Compression testing of cylindrical specimens was also carried out in the subpress using hardened flat discs separated from the test material by P.T.F.E. sheets which obviated barrelling of the specimens. Various initial strain rates were supplied by the hydraulic testing machine, and the deformation was measured by a clock dial gage resting on the cross-

Jan 1, 1970