STEELMAKING DATA SOURCEBOOK | 8 JAND BREACH dsTEELMAKING DATA SOURCEBOOK REVISED EDITION Y By The Japan Society for the Promotion of Science The 19th Committee on Steelmaking Gordon and Breach Science Publishers New York London Paris Montreux Tokyo Melbourne©1988 by Gordon and Breach Science Publishers S.A., Post Office Box 161, 1820 Montreux 2, Switzerland. All rights reserved. Gordon and Breach Science Publishers Post Office Box 786 Cooper Station New York, New York 10276 United States of America Post Office Box 197 London WC2E 9PX England 58, rue Lhomond 75005 Paris France 3:14-9 Okubo Shinjuku-ku, Tokyo Japan FBF 669. %0/. 78 Private Bag 8 Camberwell, Victoria 3124 Australia Originally published in Japanese in 1968, revised edition Published in 1984, as Recommended Equilibrium Values for Steelmaking Reactions by The Japan Society For The Promotion of Science, Tokyo. Library of Congress Cataloging-in-Publication Data Steelmaking data sourcebook. English translation of ... the revised “Recommended equilibrium values for steelmaking reactions” (1988) Cf. Pref. 1, Steel—Metallurgy. 2. Iron alloys—Metallurgy. 3. Chemical reactions. _ 1. Nihon Gakujutsu Shinkokai, Seiko Dai 19 Tinkai. II, Recommended equilibrium values for steelmaking reactions. 'TN705.884 1988 669".142 87-284 ISBN 2-88124-153-0 No part of this book may be reproduced or utilized in any form or by any means, clectronic or mechanical, inchiding photocopying and recording, or by any in- formation storage or retrieval system, without permission in writing from the Publishers. Printed in the United States of America,CONTENTS Bretacers 6 tt. de lane 9-4), Members of the Committee on Recommended Values and the Editorial Board .. List of Figures . List of Tables. . PART I. Recommended Equilibrium Values for the Reactions of Steelmaking Introduction... - 3H2(9) =H, [A] Shiro Ban-ya and Yasutaka Iguchi..........006.00.006... 5 2. 7H (9) = H(a-, 7-, 6-Fe), [A] Shiro Ban-ya and Yasutaka Iguchi ....................... u 2Na(9)-N, [A] Shiro Ban-ya and Yasutaka Iguchi 2Na(9) = N(o-, 7-, 6-Fe), [A] Shiro Ban-ya and Yasutaka Iguchi ...........¢000.-004 55. 27 . 2P2(9) =P, [A] Eiichi Kato... . 282(9) = §, [A] Rich Recto Wielbs~. anigersel coididi sad 4 Al203 = 2Al + 30, [A] Toshisada Mori, Eiji Ichise and Akira Moro-oka .....,,.. 45 B,0s(I) = 2B + 30, [0] Yasuji Kawai and Katsumi Mori..... 00.0... 0000. cc. 55 . { 9+ CO(g) = CO2(g), a 2 21 S a 2 st ~ © €+CO2(g) = 2C0(g), [A] C+0=0CO(5), [A] Yasuji Kawai and Katsumi Mori... ...........c0cc00005 59 10. O(7-Fe) + CO2(g) = 2CO(g), [A] Yasuji Kawai and Katsumi Mori..............¢c0cccc000. 73vi i. 12. 13. 14. = 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. STEELMAKING DATA SOURCEBOOK Ce203(s) = 2Ce + 30, [C] Wentiehtino Stiguki. 0.3 so iss .sh Se) Sree vache. 87 FeCr20q(s) = Fe(!) + 2Cr +40, [A] { Cr203(s) = 2Cr + 30, [B] } Shiro Ban-ya and Yasutaka Iguchi .. Fe,O(I) = tFe(t) +O, [A] Shiro Ban-ya and Yasutaka Iguchi is fae ook. 28 ili Q + H2(9) = H20(9), [A] Shiro Ban-ya and Yasutaka Iguchi Fe,O(l, 8) + Mn = MnO(l, s) + tFe(!), [A] { Mn +0 = MnO(1,5), [A] Hiroshi Sakao and Toshiharu Fujisawa NbO2(s) = Nb + 20, [A] Kiichi Narita and Toshio Onoyelit ies 35, eioliagesy 137 $i02(s) = Si +20, [A] Hiroshi Sakao and Toshiharu Fujisawa ..../8) A= He 145 TagOs = 2Ta + 50, [A] Kiichi Narita and Toshio Onoye . TisOs(s) = 3Ti +50, (C) Ken-ichiro Suzuki .. { FeV20,4(s) } V200(s) = 2V +30, [A] Hiroshi Sakao and Toshiharu Fujisawa .... 200. 0..00. 00.05 175 %02(3) = Zr + 20, [B] Shiro Ban-ya and Yasutaka Iguchi .......... 0060000000... 189 AIN(8) = Al+N, [B] Zen-ichiro Morita and Toshihiro Tanaka .. BN(s) =B +N, [C] Zen-ichiro Morita and Toshihiro Tanaka .........666000. 4. 199 NDN(s) = Nb +N, [C] Zen-ichiro Morita and Toshihiro Tanaka ...... 006600600... 205 TaN(s) = Ta +N, [C] Zew-iehiro Morita and Toshihiro Tanaka ......0........... 2u1 TiN(s) = Ti +N, [B] Zen-ichiro Morita and Toshihiro Tanaka YN(s) =V.+N, (C] Zen-ichiro Morita and Toshihiro Tanaka ..............,... 225TABLE OF CONTENTS vii 29. ZrN(s) = Zr+N, [C] Zen-ichiro Morita and Toshihiro Tanaka 30. CaS(s) = Ca +S, [C] Ken-ichiro'Suzukl 2.5 0..0S0Gi vagy asesdess buncv eons 235 31. CeS(s) = Ce +8, [B] Ken-ichiro Suzuki 32, 33. TiS(s) = Ti+S, [B] er ichitg Simul. od Sh tae Reronmiended Rae: 257 34, ZrgSa(s) = 3Zr + 48, [C] Ken-ichiro Suzuki . 35. NbC(s) = Nb + C(sat), [A] chi Narita and Toshio Onoye .... 36. TiC(s) = Ti+ C(sat), [A] Massayasu Ohtani and Hirobumi Inoue................... 269 PART Il. Recommended Values of Activity Coefficients and Interaction Parameters for Elements in Iron Alloys Tetrgductions sssctewinin, die Copomctiaelo ent 1. Activity coefficients in the infinite dilute liquid and solid iron solutions and the change of standard free energy of the reactions $(g, U2) = (1%) Veiner, Joe. Ssanineclewee . Interaction parameters in iron alloys ........ 2.1 Interaction parameters in liquid iron alloys 2.2 Interaction parameters in solid iron alloys .. 2.3 Interaction parameters in carbon saturated iron alloys... . Reference numbers 3.1 Reference numbers on the activity coefficient in infinite dilute solution 3.2 Reference numbers on the interaction parameters List of systems for which the recommended values are available . References 273 e - ax pepuauuoray pastaer oy} Jo TOTyIpe ofenSuel-ysysuq ue YIM JWeAI Sty} ayeIOMIOMITIOD 0} Poploap aa}}{UIMOD ayy, “BuPeUTTea}g U0 997 “MUMUIOD YAGT oy} Jo AvesuoatuU YING ey} PoysULA FEGT 1040120 “soouRysuMorI9 Word JopUN WoLENfeAd aye Joy MOTTE SoNyeA papusutoser asoyM splay asay) Ur syradxe Aq paptduroo sem suouponayy Susyouyoag sof sanyo, wnraqyinby papusumossy Jo uorIpe postaor AU, “SOINJOs 91} Jo staIoTJOoo AyLATIOB a} Se [Jam se ‘SopIqseD pire ‘sopymns ‘sapUytU Jo UOYeULIOT a7 epnpDut 0} papuedxe weeq Mou se aBuvs oy, “9038 Jo sjuaNgTSTOD ay} TOs soprXo Jo UOIEUTIOJ ayy 0} poxruny Ayjesomo8 ox9M sonyea peptaumiosar snoraarg ‘(oayytuMONqng suoHoREY SUDTVUTTIEIg) OBES TYSOITH rOsseorg Jo diysueULATEYD ouy sapun gz6T Areniqay UI sonfeA pepuouTMOD9yY UO aez}TEULOINE 313 paystqeyse SuppeMa07g wo aayqTUMHOD TET a astodsar wt pue ‘tor, “Ape pastaar Afaqoqdutoo & 10] spueutap SuONS aom aio) ‘SKULL, “[eLt -97euL awios Jo ZuIJeP oy} PassouyIM axeT ToNRoTGnd sqI eouTs passed aavy yey sxe0X w9y oy pure “qutrd ut ro81O] OU st WOHNTpe jeULsLIO SII ‘Joaemopy ‘SuLpeUNE}S YIM poyeroosse sioyJo pue sioUsu9 pure ‘Ar -snput [9038 ay3 UL sreyprvases £q pasn ATepIm pre poatgoas [Jam tW99q, sey suoyovay Gunyoujaarg sof sanjo, wntugyinbg papuouuooagy “SuLpeUTeayg Uo ooqyTuTMOD WET ey} Aq WoIssND -stp a[qviopisuoo zaye einmemeg TysoIF] weMETED Aq PE6T dy UE OYsTQuyse sem ooyITEMMIOD aAIyRITASMOD oY, “speLoywUT Jo AyTeNb oy SuNeNTeAd Jo sporpout ySIQeysd 09 sea aAroo[qo Axeurtad soy ‘Jog Ur SUOISNJOU] d1[[eJaUIUON UO aaqyTUTUID oALVEYNSMOD a3 Aq oUOp BUT -9q YIOM TPIM OLEIDoSse UI JNO paLttes sem Jooford oY, “SUOISN|DUL arfejouruoT Jo toreMOY aq 04 payut] Ajaso[> axe yey) suoToeET Bul =yeur[99}8 AyrJuapt 0} wayeyrapun yoaford yoresor re94-9arT]} 8 Jo [NSIT at} st suoronay Burynujaag sof sanpo, wrssgypnbyy popuaumooay -(eouarag jo uorjomorg eq} Joy Ayolo0g ueder ‘Suryeurjooyg wo aoyyruTMOD) TY6T) storey SuLyRUT]ee}g UO ooy9TUTUIODGNS PGT oy} Aq poupe ‘(896T qsn3ny :worpipe asouedes ys1y) suonovay Suxyousjaayg 4of sanjo, wines -quinby papusumuorsy ayy Jo uorppe ToBze] pue postaor Aoyo[du109 aq} Jo uoNR[suEN YsySUG ue si Yoogaosn0g vyDG Guryoujearg OU, dqovadadSTEELMAKING DATA SOURCEBOOK Eiichi Kato Professor, Waseda University, Member of the 19th Committee on Steelmaking Michio Inoue Professor Emeritus, Nagoya University, Ex-vice-Chairman of the 19th Committee on Steelmaking (1978-1980) Toshiharu Fujisawa Reader, Nagoya University Toshisada Mori Professor Emeritus, Kyoto University, Ex-vice-Chairman of the 19th Committee on Steelmaking (1973-1976) Hideji Ichise Professor, Kyoto University, Member of the 19th Committee on Steelmaking Akira Moro-oka Lecturer, Kyoto University Zen-ichiro Morita Professor, Osaka University, Member of the 19th Committee on. Steelmaking Kiichi Narita Chief Engineer, Kobe Steel Co., Ltd Ken-ichiro Suzuki Chief Research Engineer, Technology Research Center, Kawasaki Steel Corp. Yoshiharu Kawai Professor Emeritus, Kyushu University, Member of the 19th Committee on Steelmaking Katsumi Mori Professor, Kyushu University LIST OF FIGURES PART I CHAPTER 1 1. Comparison of equilibrium constant for the reaction, 3H, = H(I-Fe) (values reported before 1967) ... 2. Comparison of equilibrium constant for the reaction, 4Hy = H(-Fe) (values reported after 1967) ...........0.0 7 CHAPTER 2 1. Comparison of equilibrium constant for the reaction, 4H» = H(a-Fe) (values reported before 1967) ...........-- R 2. Comparison of equilibrium constant for the reaction 3H = H(a-Fe) (values reported after 1967)... 3. Comparison of equilibrium constant for the reaction, 4H = H(y-Fe) (values reported before 1967) .. 4. Comparison of equi 4H = H(7-Fe) (values reported after 1967) .. 5. Comparison of equilibrium constant for the reaction, 1H — H(6-Fe) perce ete ear 16 6. The solubility of hydrogen in iron at a hydrogen pressure of L atm ........2..-..00eeseeeeeeeeee 17 CHAPTER 3 1. Comparison of equilibrium constant for the reaction, 1Ng =N(U-Fe) (values reported before 1967) . 2. Comparison of equilibrium constant for the reaction ENoN(I-Fe) (values reported after 1967) ..............2... 23 CHAPTER 4 1. Comparison of equilibrium constant for the reaction 2. Comparison of equi 3. Comparison of equilibrium constant for the reaction, No =N(6-Fe) .STEELMAKING DATA SOURCEBOOK Eiichi Kato Professor, Waseda University, Member of the 19th Committee on Steelmaking Michio Inoue Professor Emeritus, Nagoya University, Ex-vice-Chairman of the 19th Committee on Steelmaking (1978-1980) Toshiharu Fujisawa Reader, Nagoya University Toshisada Mori Professor Emeritus, Kyoto University, Ex-vice-Chairman of the 19th Committee on Steelmaking (1973-1976) Hideji Ichise Professor, Kyoto University, Member of the 19th Committee on Steelmaking Akira Moro-oka Lecturer, Kyoto University Zen-ichiro Morita Professor, Osaka University, Member of the 19th Committee on Steelmaking Kiichi Narita Chief Engineer, Kobe Steel Co., Ltd Ken-ichiro Suzuki Chief Research Engineer, Technology Research Center, Kawasaki Steel Corp. Yoshiharu Kawai Professor Emeritus, Kyushu University, Member of the 19th Committee on Steelmaking Katsumi Mori Professor, Kyushu University LIST OF FIGURES PART I CHAPTER 1 1. Comparison of equilibrium constant for the reaction, 1H = H(l-Fe) (values reported before 1967) ... 2. Comparison of equilibrium constant for the reaction, 1H = H(L-Fe) (values reported after 1967) .............0. 7 CHAPTER 2 1. Comparison of equilibrium constant for the reaction, 2H = H(a-Fe) (values reported before 1967) ........--.-- R 2. Comparison of equilibrium constant for the reaction 4H = H(a-Fe) (values reported after 1967). . 3. Comparison of equilibrium constant for the reaction, 4H = H(y-Fe) (values reported before 1967) .. 4. Comparison of equi 4H = H(7-Fe) (values reported after 1967) .. 5. Comparison of equilibrium constant for the reaction, 4H — H(6-Fe) Baten etre oe 16 6. The solubility of hydrogen in iron at a hydrogen pressure of 1atm ..........0s.ceeeseeeeeeeees 17 CHAPTER 3 1. Comparison of equilibrium constant for the reaction, 1Ng = N(U-Fe) (values reported before 1967) . 2. Comparison of equilibrium constant for the reaction 4NeN(I-Fe) (values reported after 1967) ................2. 23 CHAPTER 4 1. Comparison of equilibrium constant for the reaction 2. 3. Na =N(6-Fe) ...xiv STEELMAKING DATA SOURCEBOOK 4, The solubility of nitrogen in iron at a nitrogen ireusarSloPl tends ot, Siecle. call Cathe doe outhtvw ; CHAPTER 5 1. Equilibrium constant for the reaction }P,(g) = P and the partial pressure of P in equilibrium with the Fe-P alloy containing P at its standard state .. 2. Vapor pressures of P, P2 from Fe-P alloys at 1600°C. CHAPTER 6 1, Equilibrium constant for the reaction $8 + Ho(g) = H2S(g) .. 2. Equilibrium constant for the reaction 4S2(g) =S and the partial pressure of Sp in equilibrium with the Fe-S alloy in which sulfur is at its standard state CHAPTER 7 1, Comparison of the K values of the reaction: AloOs(s) = 2A1+ 30 (numbers are equivalent to the references) . 2. Comparison of the K values of the reaction: Al2Os(s) 2Al +30 (numbers are equivalent to the references) . CHAPTER 8 1, Equilibrium constant for the reaction B2O3(l) = 2B +30 .. CHAPTER 9 1, Equilibrium constant, Ay, for the reaction O + CO = CO3.. 2. Equilibrium constant, Ko, for the reaction C + CO2 = 2CO. 3. Equilibrium constant, Ky, for the reaction 0 + CO = CO2 (data reported after 1959) 4, Equilibrium constant, Ko, for the reaction C CO (data reported after 1959) 5, Equilibrium constant, 3, for the reaction C +O = CO CHAPTER 10 1. Comparison of values of 72 2. The dependency of log jq on the mole fraction of carbon in >-Fe (1273K) CHAPTER 11 1. Equilibrium constant of the reaction; CaO(s) =Ca+O .... 2. Relation between solubility product and concentration inn terms of [MCa) 2-5 [260 ]ia wenn. anatase Lage de. aeidnnncen CHAPTER 12 1. Relation between equilibrium oxide phase and activities of oxygen and sulfur (Wilson, Kay and Vahed [4])............ 2. Equilibrium constant for the reaction: Keg Os (4) — Gerd SOW yews swageeu ee sccuns eocieen esl 31 - 36 - 37 40 gral - AT OL 56 60. 61 Ok . 63 . 64 74 . 7 81 LIST OF FIGURES x 3, Relation between apparent equilibrium constant for the reaction: Ce203(s) = 2Ce + 30, and 3[%Ce] + 17.5[%O].... 90 CHAPTER 13 1. Comparison of equilibrium constant for the reaction, FeCr20q(s) = Fe(!) +2Cr+40 (values reported before 1967) ........+.04e0eeeeeeeeee eee 97 2. Comparison of equilibrium constant for the reaction, FeCr2Oa(s) = Fe(!) + 2Cr + 40 (values reported after 1967)......6..cs0eesesseeeeeeee eee 100 . Relationship between log([%Cr]?[%O]*) and (%Cr] at 1873K . . Relationship between log([%Cr]*[%0] [96Cx] at 1873K ... 5. Comparison of equilibrium constant for the reaction, Gre) aCe BO ee og rare 108 CHAPTER 14 1. Relations between solubility of oxygen in liquid iron and temperature (values reported before 1967) 2. Relations between solubility of oxygen in liquid iron and temperature (values reported after 1967) ...............++ 113 CHAPTER 15 1, Comparison of equilibrium constant for the reaction, O+Hp = H20 (values reported before 1961) .. 2. Comparison of equilibrium constant for the reaction, 0+ Hy = H20 (values reported after 1961) . CHAPTER 16 1. Equilibrium constant for the reaction, Fe,O(l) +Mn =MnO(l) + t8e(!) .....5.2..peceeeeeeee eee 127 2, Equilibrium constant for the reaction, Fe,(s) + Mn = MnO(s) + tFe(1) .. 3. Equilibrium constant for the reaction, Mn + 0 = MnO(I) 4, Equilibrium constant for the reaction, Mn + O = MnO(s).. . 133 CHAPTER 17 1, Equilibrium constant for the reaction NbO(s) = Nb + 20. . 138 2. Relationship between e? and temperature ‘ CHAPTER. 18 1. Equilibrium constant K (or K") for the reaction, Si02(s) = Si +20 2 axvi STEELMAKING DATA SOURCEBOOK CHAPTER 19 1. Equilibrium constant for the reaction TazOs(s) = 21a + 50 2. Equilibrium relationship between [%Ta] and 3. Relationship between ef2 and temperature 4, Relationship between ¢S* and temperature CHAPTER 20 1, Relation among equilibrium deoxidation product, [COLI] rand gyal (27d 8 Rina nea AO cadastral 166 2. Relation between eG! and range of titanium content at which ¢3! is determined - 167 3. Equilibrium relation in liquid Fe-Ti-O system . - 169 4, Equilibrium constant for the reaction; Tiss — 32i+50 ... 170 CHAPTER 21 1, Equilibrium constant Ky = a2, - a for the reaction, FeV20a(s) = Fe(l) + 2V. +40 (before 1964) .............5 179 2. Equilibrium constant Kz = a2, - a, for the reaction, V20s(s) = 2V + 30 (before 1964) 3. Equilibrium constant Ky = a%, - a6 for the reaction, FeV204(s) = Fe(!) + 2V. + 40 (after 1964)... 4, Equilibrium constant Ke = a2, - a3, for the reaction V203(s) = 2V + 30 (after 1964) ©0202. 2. 185 CHAPTER 22 1, Relations between log K(K’) and temperature ............ 191 CHAPTER 23 1, Relationship between log K and temperature for the reaction AIN(s) = Al+.N 2. Relationship between log f(t! and [9%Al] (1873K) 3. Relationship between ef! and temperature . CHAPTER 24 1. Relationship between log K and temperature for the reaction BN(s) =B+N : = 200 2. Relationship between log /@ and [%B] (1873K) . - 202 3. Relationship between eB and temperature .. 103 CHAPTER 25 1. Relationship between log K and temperature for the reaction NbN(s) =Nb+N . cytes 208 2. Relationship between log /X® and [%Nb] (1873K). - 208 LIST OF FIGURES avi 3. Relationship between eX and temperature ++. 209 CHAPTER 26 1. Relationship between log KC, log K’ = [%6Ta][%N] and temperature for the reaction TaN(s) =Ta+N .. 212 .214 2. Relationship between log /Z* and [Ta] (1873K) @ - 215 3. Relationship between e4* and temperature .. CHAPTER 27 1, Relationship between log K and temperature for the reaction TiN(s) =Ti+N = 218 2. Relationship between log fq! and [%Ti] (1873K) . . 220 3. Relationship between ef! and temperature..........+-++++ 221 CHAPTER 28 1. Relationship between log K and temperature for the reaction WING) Va cau eaetel lig nu een ead eect attic 2. Relationship between log f¥ and [%V] (1873K) 3. Relationship between eX and temperature ... CHAPTER 30 1, Equilibrium constant for the reaction CaS(s) = Ca+S .....236 2. Precipitation diagram for liquid Fe-Ca-O-S system, 1873K 20.2.0... 02 eee eee seen eee e eee 238 3. Relation between log K’ for the reaction CaS(s) = Ca+$ and [%Ca] + 1/25|%S].......2ee2222000- 239 CHAPTER 31 1. Effect of CeS lining on sulfur contents in quenched ingot [7] 2. Relation between apparent equilibrium constant and concentration in terms of [%Ce] + 4.37[%S] 3. Rearrangement of experimental results by taking strong interaction between cerium and sulfur in the melt into account 4, Equilibrium constant: for the reactio: CHAPTER 32 1. Relation between apparent equilibrium constant, Kj, and concentration in terms of [%La] + 4.34[%S] ......-..- 5 2. Equilibrium constant for the reaction: LaS(s) =La+$ CHAPTER 33 1, Equilibrium relation in liquid F2~Ti-S system...........4+ 258 2. Relation between apparent equilibrium constant, K’ and concentration in terms of [%Ti] + 1.49[%S] - 249 250 » 254xviii STEELMAKING DATA SOURCEBOOK CHAPTER 34 1. Equilibrium relation in liquid Fe-Zy-S system............. 262 CHAPTER 35 1. Effect of niobium on the solubility of carbon in liquid iron .. 267 CHAPTER 36 1. Equilibrium constants on the reaction TiC(s) = Ti+ C(s) ..271 PART I No figures. LIST OF TABLES PART I CHAPTER 1 1. The Values for Equilibrium Constants and Its Temperature Pareto 25 PEP Oe is DUETS, SN, 6 ae PRU Pale 8 CHAPTER 2 1. The Values for Equilibrium Constants and Its Temperature AneLONs 22... :00H2geH1 od ser aanionetl SRO ny 18 CHAPTER 3 1. The Values for Equilibrium Constants and Its Temperature Functions . 24 CHAPTER 4 1. The Values for Equilibrium Constants and Its Temperature Functions awe CHAPTER 5 1. Equilibrium Constant for the Reaction $P2 = CHAPTER 6 1. Equilibrium Constant for the Reaction S + H2 = HS esr 42 CHAPTER 7 1. Comparison of the Equilibrium Constant .....-..++++++-++ 48 CHAPTER 8 1. Values for Equilibrium Constant, K, or Apparent, Equilibrium Constant, Ten 2. Comparison of Interaction Parameters .. CHAPTER 9 1. Values for Equilibrium Constant, K1, and Its Temperature Function .. 65 2. Values for Equilibrium Constant and Its Temperature Function 66 3. Values for Equilibrium Constant, Ks or Kj . . 7 4. Values for Interaction Coefficients, f§, or Interaction Parameters, eG... 0.2 .c0ecteeesecseeseieneee eee redete 68xx STEELMAKING DATA SOURCEBOOK 5. Values for Interaction Coefficients, /§, or Interaction Parameters, ¢ CHAPTER 10 1. Activity Coefficient of Carbon in Austenic Iron (qe and 4G: Referred to Graphite and Infinite Dilution) .... 76 CHAPTER 11 BARES Ce Sr Re GacOs0. 8 2 aaah ikea aves 83 CHAPTER 12 1. Literature Survey on Equilibrium Relations in Fe~Ce-O and Fe-Ca-O-S Systems . . 91 Cree 13 1. Equilibrium Oxide Phases in the Fe-Cr-O System......... 98 2. The Values for Equilibrium Constants and Its epee i ee for the Reaction, FeCr204(s) = Fe(l) + 2Cr +40. 101 3. Interaction Bee ae - 102 4. The Values for Equilibrium Constants and Its Temperature Functions for the Reaction, Cr203(s) = 2Cr +30 . -- 107 CHAPTER 14 1. Solubility of Oxygen in Liquid Iron . CHAPTER 15 1. The Values for Equilibrium Constants and Its Temperature Functions : : 2. Interaction Parameters . CHAPTER 16 1. Equilibrium Constants 130 2. Interaction Parameter eM? 3. Interaction Parameter ef” CHAPTER 17 1. Comparison of Values for Equilibrium Constant . 2. Comparison of Values for Interaction Coefficient . CHAPTER 18 LBquilibrium Constant Foo... seen os sn. on pv eettemae 148 2. Interaction Parameter e&} at 1873K . 3. Interaction Parameter ¢8! at 1873K . CHAPTER 19 1. Comparison of Values for Equilibrium Constant .. 2. Comparison of Values for Interaction Coefficient . .. 140 .- 160 ». 161 LIST OF TABLES 20d CHAPTER 20 1. Relation between Deoxidation Product and Titanium Content. 2. Measured and Estimated Values of 79 3. Outline of Equilibrium Measurement of Fe TigOs(s) or TigQa(s) as Deoxidation Product. CHAPTER 21 1. Equilibrium Constants Ki and K2 2. Activity Coefficients and Interaction Parameters . . CHAPTER 22 1. The Values for Equilibrium Constants and Its Temperature Functions .......-.- ‘ O System with -176 - 180 +192 2. Interaction Parameter CHAPTER 23 1. Comparison of Equilibrium Constant and Interaction Parameter for the Reaction AIN(s) = AI4+N......-....645 195 CHAPTER 24 1. Comparison of Equilibrium Constant and Interaction Parameter for the Reaction BN(s) =B+N . - 201 CHAPTER 25 1. Comparison of Equilibrium Constant and Interaction Parameter for the Reaction NbN(s) =Nb+N.......-..-++ 207 CHAPTER 26 1, Comparison of Equilibrium Constant and Interaction Parameter for the Reaction TaN(s) =Ta+N . CHAPTER 27 1. Comparison of Equilibrium Constant and Interaction Parameter for the Reaction TiN(s) = Ti+ N............-. 219 CHAPTER 28 1, Comparison of Equilibrium Constant and Interaction Parameter for the Reaction VN(s) =V+N... CHAPTER 29 1, Comparison of Equilibrium Constant and Interaction Parameter for the Reaction ZrN(s) =Zr+N........--..4- 234 CHAPTER 30 1. Literature Survey on Equilibrium Relation in Fe-C: "iieeieZo) eager al Regge An ee a - 237sedi STEELMAKING DATA SOURCEBOOK CHAPTER 31 la. Outline of Equil CaS(s) =Ce+S 1b, Thermochemical Evaluation of Equilibrium Relation in Fe-Ce-S System 2. Relation between Value of Equilibrium Constant and Range of [%Ce] + 4.37[%9] at which the Constant is Determined... 24 3. Thermochemical Quantities in Fe-j-S Systems Determined iby Rijiiries eb ale. gsc choc betes TF el ccna 246 CHAPTER 32 1. log K, 78.) e£3, and ey* Experimentally Determined ys Sag RU le cougar 9 i NE 254 CHAPTER 33 1. log K and ef! Experimentally Determined at 1873K ....... 258 CHAPTER 34 1. log K and e&* Experimentally Determined by 1873K ......- 263 CHAPTER 35 1. Comparison of K’ and efx, CHAPTER 36 1. Temperature Dependency of Solubility of Titanium in the Carbon Saturated Liquid Iron . 2. Equilibrium Constants on the Reaction, MGT ROC Sve neta ey no= leat 5 272 PART II 1. Activity Coefficients in the Infinite Dilute Liquid and Solid Tron Solutions and the Change of Standard Free Energy of the Reaction: i(g, 1,8) = i(1%) » 278 2.1. Interaction Parameters in 280 2.2. Interaction Parameters in Solid Iron Alloys. . 294 2.3. Interaction Parameters in Carbon Saturated Iron Alloys . . 296 3.1. Reference Numbers on the Activity Coefficient in Infinite Dilute Solution aay 3.2. Reference Numbers on the Interaction Parameters ....... 298 4, List of Systems for which the Recommended Values is Available . rium Measurements for the Reactio1 Part I Recommended Equilibrium Values for the Reactions of SteelmakingPart I. Recommended Equilibrium Values for the Reactions of Steelmaking Introduction Equilibrium values for 36 reactions of steelmaking are recommended and provided in Part I. The system of notation is explained as follows, for the reader’s convenience. 1. Reaction Formula For example, the deoxidation reaction with aluminum is usually ex- pressed as 2Al + 30 = AlzO;(s). In this book, however, it is con- ventionally expressed as AlzO3(s) = 2Al + 30, as the deoxidation constant is expressed K = a3, - a3. The other cases such as nitrides also follow the above example with some exceptions. 2. States of Reactants and Reaction Products Ha(g), P2(g), ete.: gaseous hydrogen and phosphorus, ete. H, N, ete.: hydrogen and nitrogen dissolved in liquid iron, ete. Al203(s), B2Os(l), ete.: solid AlgOs and liquid ByOz, etc. 3. Accuracies ‘The recommended equilibrium values were classified into three ranks A, B, and G, on the basis of their accuracies, and the following sym- bols, [A], [B], and [C], were attached after the reaction formula in the subtitle of each chapter: (ex) 3H2@)=H, [A] a2) SHIRO BAN-YA and YASUTAKA IGUCHI ‘The classifications have been made somewhat qualitatively based on the following standards: [A] ‘The method of the experiment and the results are highly reliable, so that serious modifications may not be required, even if new studies are presented in future. [B] The values do not deserve [A], because of insufficient reliability of the experimental method and the results. [C] The reliability of the experimental method and the results could not be evaluated, and the values should be regarded as only ref- erence data. 4. Units The unit of energy used in this book, such as AG, is [J]. As almost all the available data in the literature cited in this book were given in [cal], the following equations have been used to make the transfor- mation from [eal] to [J]. 1 cal = 4.184 J AG? = -19.144T log K 5. Activities of Reactants and Reaction Products i. Solute Activities in Iron Base Alloy Unless otherwise indicated, the reference state of solute activity is the infinitely dilute solution of iron base alloy. The solute content is expressed in terms of weight percent. fi and f; denote the activities of elements i and j, and fi, fi, fi, and {2 denote the interaction coefficients of i and j on é and j in iron base alloy, respectively. e! and r] denote the first- and the second-order interaction parameters. ‘The activity coefficient in Fe-é-9 system is expressed, in most cases, by the following relationship: log fi = log f} +log 7 = ey[6i] + €{[%] Prt. I: Recommended Equilibrium Values for the Reactions of Steelmaking 3 Only when the concentration of j is fairly high, such as the case of the reaction of nitride formation, it is expressed by, log fi = e4[%i] + ef [%g] +13 [%a]? ii. Activity of Iron In case when iron participates into the reaction, are appears in the notation of the equilibrium constant. As far as the solute contents in iron alloy are sufficiently low, it can be regarded that ape is approx- imately fixed, and it is omitted from the notation of the equilibrium constant. When the solute contents are fairly high, such as the case of FeCr04(s), it is approximated by are = Cre = %Fe/100. iii, Activities of Oxides and the Other Chemical Compounds ‘The standard state of the activity is the pure substance, and mole fraction being concentration coordinate. 6. References ‘The references consulted iu Part I were listed at the end of each chap- ter of reaction system. Hence, some of them were quoted repeatedly with different reference number in various reaction systems. On the other hand, it is to be noted that all references consulted in Part II were listed all together with serial reference number. ‘The literature survey has been made throughout the references which have been reported by the middle of 1983, with a few excep- tions.1. 5H(9) = H, [A] SHIRO BAN-YA and YASUTAKA IGUCHI Faculty of Engineering, ‘Tohoku University, ‘Aza Aoba, Aramaki, Sendai-shi, Miyagi-ken 980 Japan I. Recommended Values 7Ha(g) = H(L-Fe) @ K = an/V/Pa, 5 [%H)/V Pa, (2) log K = ~1,905/T — 1.591 (3) AG? = 36,460 + 30.467 (4) where Py, is the partial pressure of hydrogen designated with atm, and the activity of hydrogen ay is based on the reference state of the infinitely dilute solution of hydrogen in pure liquid iron and the concentration in mass percent. Since hydrogen dissolved in liquid iron obeys Sieverts’ law, the activity and activity coefficient of hydrogen in metal can be expressed with an = [%H] and fff =1. I. Explanatory Remarks ‘The Equations (1)-(4) are the relationships adopted from the formu- lae presented by M. Weinstein and J. F. Elliott. ‘The solubility of hydrogen in liquid iron first was studied system- atically by A. Sieverts and his co-workers (1, 2], and a number of the investigations were repeated by many researchers [3-24] since that. ‘The experimental results reported until the selection of previous rec- ommended values in 1967 were compared in Fig. 1. Two different kinds of the experimental methods have been tried for the measure- ment of the solubility of gases in metal, the sampling method and the 58 SHIRO BAN-YA and YASUTAKA IGUCHI ‘Table 1 The values for equilibrium constants and its temperature functions Ref. Author Equilibrium Constant Procedure 3 Yajima log K = -2,361/: i ~2,361/T — 1.3484 Sieverts’ method 4 Karnaukh Kamaukhov and log K = -1,745/T — 1.718 _Sieverts’ method 7 Busch and Dodd log K = —2,572, 1873K _Sieverts’ method 9 Maekawa and log. K = -880/T—2.155 Sampling method Nakagawa ae 10 Schenck and Wunsch log 11 Weinstein and Elliott log K »370/T — 1.930 Sampling method :905/T — 1.591 Sieverts’ method Cea : value 12 Gunji, Me = i oa Moree log K = -1,700/T — 1.694 Sieverts’ method 13 Matoba, Fuwa, log K = ~1, =, ieverte? Beieaineee ae ,900/T — 1.577 Sieverts' method ‘Ono 15 Kato, Fuk =- i ag? Fukuda and log K = -1,874/T—1.601 Sieverts’ method 16 Luckemeyer- K= Calculation Hasse and Schenck 2.75 10-®¢°C-1755x10-5 AT Geller and Tak-Ho log K = -1,637/T - 16.84 Calculation Sun 18 Nagasaki, = i Ragesaki, Someno log K = —1,880/T— 1.605 Sieverts’ method 19 Yakushev, Yavoiskiy log K = — ieverts’ Jepeter Serdar toe 2,607, 1833K —_—_Sieverts’ method 20 Yakush =+ i ee and log K = ~1,850/T — 1.59 Sieverts method ZA Schenck and Lange log K = ~1,662/T— 1.781 _Sieverts’ method Kostina, Baum, log K = ~1,570/T — 1.7056 Sieverts’ method Kurochkin and Géld 23 Petrushevsky, Géld, K=-1 - i Potrasheraky, Gaia, Jog 985/T ~ 1.7263 Calculation 24 Ngia, Yavoiskiy, log K = — = ieverts’ Deas Yee log. 1,639/T — 1.73 Sieverts’ method Afanaséy S091 sav of the dead volume, and the improvement of the ay Purity of the metal used. As shown in Fig. 1, the erperimenel ders obtained by M. Weinstein and J. F. Elliott [i], K. Gunji et al (13 S. Matoba et al. [13], ‘T. Bagshaw et al. [14], A. Kato et al. [15], and H. Nagasaki et al. [18], who employed the modified Sieverts’ method are in very good agreement with each other within the experimental errors of 0.5 ml/100 g and the relative errors of ++15% for the real solubility. The disagreement on the solubility of hydrogen in liquid Ch. 1: $H2(9) = H, [A] 9 iron is very small among these investigations. Therefore, the experi- mental results by M. Weinstein and J. F. Elliott [11] reported earliest was selected as the recommended values in 1967. Other experimental data reported since the selection of the previ- ous recominended values in 1967 were shown in Fig. 2. The results obtained by A. M. Yakushev et al. [19, 20], T. K. Kostina et al. [22], and M. S. Petrushevsky et al. [23] are somewhat higher, but other results except for these four data agree well with the recommended values. Since the reasons that the measurements by these four groups were especially accurate were not found from their papers, it was concluded that there was not necessity to revise the previous recom- mended values for the Fe-H system. ‘All of the experimental results obtained by the previous investiga- tors are listed in Table 1. References [1] A. Sieverts: Z. Phys. Chem., A77 (1911), p. 591. [2] A. Sieverts, G. Zapf and H. Moritz: Z. Phys. Chem., A183 (1939), p. 19. [3] T. Yajima: Totsu-to-Hagané, 30 (1945), p. 221. [4] M. M. Karnaukhov and A. N. Morozov: Inv. Akad. Nauk SSSR, Otd. Tekhn. Nauk, Dec. (1948), p. 1845. [5] H. Liang, M. B. Bever and ©. F. Floe: Trans. Met. Soc. AIME, 167 (1946), p. 395. (6] K. T. Kurochkin, P. E. Nizhelskii and P. V. Umrilhn: Izv. Akad. Nauk SSSR, Otd. Tekbn. Nauk, Feb. (1957), No. 2, p. 19. [7] T. Busch and R. A. Dodd: ‘Trans. Met. Soc. AIME, 218 (1960), p. 488. [8] F. De Kazinczy and O. Lindberg: Jernkontoret’s Ann., 144 (1960), p. 288. [9] S. Mackawa and W. Nakagawa: J. Japan Inst. Metals, 25 (1961), p. 573. [10] H. Schenck and H. Wunsch: Arch. Hisenhiittenw., 32 (1961), p. 779. [11] M. Weinstein and J. F. Elliott: Trans. Met. Soc. AIME, 227 (1963), p. 382. [12] K. Gunji, S. Matoba and K. Ono: J. Japan Inst. Metals, 28 (1964), p. 59. [13] S. Matoba, T. Fuwa, 8. Ban-ya, H. Nozaki and K. Ono: Tetsu-to-Hagané, 52 (1966), p. 1823. [14] T. Bagshaw, D. Engledow and A. Mitchell: JISI, 203 (1965), p. 160. [15] E, Kato, $. Fukuda and Y. Nishi: Tetsu-to-Hagané, 51 (1965), p. 1830. [16] L. Luckemeyer-Hasse and H. Schenck: Arch. Eisenhiittenw., 6 (1932), p. 209. [17] W. Geller and Tak-Ho Sun: Arch. Eisenhiittenw., 21 (1950), p. 423. [18] H. Nagasaki, M. Someno and K. Kadboi: J. Japan Inst. Metals, 31 (1967), p. 729. {19] A. M. Yakushev, V. I. Yavoiskiy and Yu. V. Kryakovskii: lav. Vyssh. Ucheb. Zaved. Chern. Met., 4 (1961), No. 7., p. 44. (20] A. M. Yakushev and V. I. Yavoiskiy: Izv. Vyssh. Ucheb. Zaved. Chern. Met., 5 (1962), No. 2, p. 52. {21] H. Schenck and K. W. Lange: Arch. Eisenhiittenw., 37 (1966), p. 739. (22] T. K. Kostina, B. A. Baum, K. T. Kurochkin and P. V. Geld: Russ. J. Phy. Chem., 45 (1971), No. 4, p. 453.10 SHIRO BAN-YA and YASUTAKA IGUCHI [23] M. S. Petrushevsky, P. V. Geld, B. A. Baum and T. K, Kostina: Izv. Akad. Nauk SSSR, Metally, 2 (1971), p. 59. {24] N. Neia, V. I. Yavoiskiy, L. B. Kesterev and M. I. Afanasév: Izv. Akad. Nauk SSSR, Metally, 4 (1972), p. 18. Per 5Ho(g) i H(a-, om 6-Fe), [A] SHIRO BAN-YA and YASUTAKA IGUCHI Faculty of Engineering, ‘Tohoku University, ‘Aza Aoba, Aramaki, Sendai-shi, Miyagi-ken 980 Japan Recommended Values 3Ha(9) = H(o-,7-, 6-Fe) K = an/\/Pa, = (%H)//Pa, }Ha(9) = H(a-Fe) log K = -1,418/T — 2.369 AG® = 28,650 + 45.357. 4Ha(9) = H(7-Fe) log K = —1,182/T — 2.369 AG? = 22,630 + 45.35T }H2(9) = H(6-Fe) log K = —1,418/T — 2.369 AG® = 28,650 + 45.357" Explanatory Remarks uw (7) (8) where the definition of the partial pressure and the activity of hydro- gen is the same as the case of liquid Fe-H system. ‘The solubility of hydrogen in solid iron first was studied systemati- cally by A. Sieverts [1, 2], and a number of the investigations were repeated by many researchers [3-22] since that, as similar to the case of the liquid Fe-H system.12 SHIRO BAN-YA and YASUTAKA IGUCHI £ 900 __700 500 300 -35) aE 00 Wppr w mi/100g nN “8 ba -40 log K -45) 8 10 12 14 16 18 ml 10/T/K 2 Sieverts 11 Vv Andrew, Lee and Quarrell 4 — Sieverts, Zapf and Moritz 12 Armbruster and Austin 6 @ Iwase and Fukushima 13 + Yajima 7 © Matin 14 — Davies and Bvans 8 ~— Luckemeyer-Hasse O Sieverts’ method and Schenck @ Sampling method 9 x Pihlstrand 15 Eichenauer, Kunzig and Pebler 10 A Baukloh and Miiller 17 Geller and Tak-Ho Sun, Recommended value Figure 1 Comparison of equilibrium constant for the reaction, 1H2 (values reported before 1967) H(a-Fe) 1. Solubility of hydrogen in a-iron ‘The recommended values on the solubility of hydrogen in @-iron were & Gh, 2: }Ha(9) = H(a- +, 6-Fe), [A] > mi/100g nN log K 8 10 12 14 16 18 10/7/K" 17 _ Geller and Tak-Ho Sun, Recommended value 19-1 Blake, Jordom and Pumphrey, Cylindrical samples 19-2 Blake, Jordom and Pumphrey, Turning samples 20-2 Moro-oka, Sawada and Mori Figure 2 Comparison of equilibrium constant for the reaction 4H2 = H(a-Fe) (values reported after 1967) taken up from the selected values summarized by W. Geller and Tak- Ho Sun. ‘The experimental data reported until the selection of the previ- us recommended values in 1967 were compared in Fig. 1. The ex- perimental results obtained by A. Sieverts [2], E. Martin [7], and L. Luckemeyer-Hasse et al. [8] were in good agreement with each