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STAINLESS STEEL MAKING

Harry Brearley of Sheffield

Thomas firth & sons and John & Co

B#2$s & R#%$s

Introduction

In 1&13 Harry Brearley of Sheffield de'elo(ed )hat is )idely re*arded as the first +r,st less$ or stainless steel a (rod,-t that re'ol,tionised the metall,r*y ind,stry and .e-ame a ma/or -om(onent of the modern )orld0 He .e*an his -areer in the steel ind,stry at the a*e of t)el'e as a la.o,rer in a lo-al steel )or1s

 Steel -ontain not less than 10 12 2 Cr )ith or )itho,t

alloyin* element3!i4 Mo4 C,4 S4 Ti4 !.4 !4et-50  SS are *enerally -hosen )here -orrosion and o6idation resistan-e is im(ortant "o) S7#  In .esides 4 often ha'e *ood -ree( stren*th as -ross sli( of s-re) dislo-ation is diffi-,lt0  Cr forms a (assi'e film on steel s,rfa-e Corrosion

resistan-e is im(arted .y the formation of a (assi'ation layer -hara-teri8ed .y9
3i5 Insol,.le -hromi,m o6ide film on the s,rfa-e of the metal 3Cr2:35 0 3ii5 ;e'elo(s )hen e6(osed to o6y*en and im(er'io,s to )ater and air0 3iii5 S,s-e(ti.le to sensiti8ation4 (ittin*4 -re'i-e -orrosion and a-idien'ironments0 3i'5 <assi'ation -an .e im(ro'ed .y addin* !i4 Mo & =0

Stainless steels may -lassified as

AISI -lasses for SS9
200 300 >00 @00 B00 series series series series series ? ? ? ? ? Cr4 !i4Mn Cr4 !i !on Ma*netiCr only lo) Cr A122 <re-i(itation hardened series 3

Most (o(,lar SS is the 1%2 Cr and %2 !i 4 7erriti- SS "o) -ar.on other)ise Cr23CB inter*ran,lar -orrosion0

Ceneral <ro(erties of Stainless Steels
Electrical Resistivity
S,rfa-e & .,l1 resistan-e is hi*her

Coe icient o Thermal

E!pansion
Creater -oeffi-ient than

than that for (lain -ar.on steels

Thermal Conductivity
A.o,t >0 to @0 (er-ent that of (lain

(lain -ar.on steels

-ar.on steel

"igh Strength
#6hi.it hi*h stren*th at

Melting Temperature
<lain -ar.on91>%0 1@>0 Martensiti-9 1>00 1@30 7erriti-9 1>00 1@30

DC DC

room and ele'ated tem(erat,res

DC DC

A,steniti-9 13E0 1>@0

Sur ace #reparation
S,rfa-e films m,st .e

remo'ed (rior to )eldin*

Spot Spacing
"ess sh,ntin* is o.ser'ed

than (lain -ar.on steels

#roperties o Stainless Steel
Electrical Resistivity Thermal Conductivity Melting Temperature <lain -ar.on91>%0 1@>0 DC Martensiti-9 1>00 1@30 DC 7erriti-9 1>00 1@30 DC A,steniti-9 13E0 1>@0 D Coe icient o Thermal E!pansion "igh Strength Sur ace #reparation Spot Spacing

:6y*en lan-in* of stainless steel .ath for

de-ar.,ri8ation )as first introd,-ed in 1&3&0ori*inally it )as meant to remo'e -ar.on .elo) the reF,ired le'el )itho,t re*ard to o6idation of -hromi,m Before 1&E04The ma/ority of SS )ere made in #A7 "ater4 SS are (rod,-in* .y #A7A:; /=:; A((li-ation 9 32005 Chemi-al ind,stry4 sanitary fittin* & ho,se hold 3>005 Ho,se hold4 .lades4 1ni'es & trans(ortation 3@005 C,tlery 4s,r*i-al instr,ments and hi*h F,ality .all .earin* 4n,-lear (lants4 shi(s & steel

t,r.ine .lades

#hysicochemical principle

#llin*ham ;ia*ram 3<-o? 1 atm5
0

C)*+,C*+

$G % &c al
2 +11

+C )*+,+C* -./ Cr)*+,+./ Cr+*/

0++1

T'%C(

>/3Cr Go2 ? 2/3 Cr2:3 2CG:2 ?2C: A.o'e the eF,ation are in eF,ili.ri,m at 1220 C 3C:G2Cr ? Cr2:3G3C HC ?0 Minim,m reF,ired tem(erat,re is m,-h a.o'e than 1220 C I 1 atm0 thermodynami- & 1ineti-s so 1%00 C not 1220C

Limitation o classical process
10 A hi*h 2 of SS s-ra( -ant .e ,sed in -har*e 20 :nly "C 7erro-hrome )hi-h is F,ite -ostly -an .e ,sed for ad/,stin* the finishin* -om(osition 30 At the tem(erat,re of 1%00 C and a.o'e 0dama*e to f,rna-e refra-tory linin* is se'ere >0A -om(lete heat ta1es a.o,t % ho,rs from -har*in* to finishin* 0this restri-ts (rod,-ti'ity of the f,rna-e

Modern technology
To -arry the de-ar.,ri8ation at lo) tem(erat,re )itho,t o6idi8ation of -hromi,m0 Th,s a te-hnolo*y )hi-h -an ,se hi*h -ar.on ferro -hrome and to de-ar.,ri8e the .ath at sele-ti'ely lo)er tem(erat,res )o,ld .e reF,ired0 "o) (rod,-tion -ost Red,-tion in (ress,re of C: -an .e a-hie'ed either .y 'a-,,m or .y ,sin* a mi6t,re of ArG:20

In a-t,al (ra-ti-e 4red,-tion of <-o may effe-ted .y either .y maintainin* a lo) 'a-,,m at time of .lo)in* :2 into melt or .y mi6in* ar*on )ith :2 so e'ol'in* from the .ath is dil,ted .y Ar*on The te-hniF,es .ased on =a-,,m :6y*en ;e-ar.,ri8ation Ar*on :6y*en ;e-ar.,ri8ation

Argon *!ygen 3ecar4uri5ation

<ro-ess )as (atented .y Ind,strial *ases di'ision of ,nion -ar.ide -or(oration0 <ro-ess )as ori*inally de'elo(ed for the (rod,-tion SS only0 "ater it )as e6tended to the man,fa-t,re of lo) alloy and tool steel as )ell0 In A:; -on'erter4 ar*on is ,sed to dil,te the other *aseo,s s(e-ies To red,-e the (artial (ress,re of Car.on Mono6ide 0 >/3Cr Go2 ? 2/3 Cr2:3 2CG:2 ?2C: effe-t of (ress,re

S&etch o A*3

Molten -har*e from ar- or ind,-tion f,rna-e is transferred to this 'essel and .lo)n )ith Ar J o6y*en mi6t,re0 In sta*e 1 :6y*en to ar*on ratio is 391 )hen -ar.on is red,-ed to 302 In sta*e 2 the ratio red,-ed to 291 .ath .lo)n to a.o,t 000& 00122 -ar.on In sta*e 3 a 192 .lo) red,-e the -ar.on to as lo) as 0002 2 Ma/or -han*e in .lo)in* (ra-ti-e has .een dire-t s,.stit,tion of nitro*en for ar*on thro,*ho,t sta*e 1

Thermodynamics o reaction in A*3

"i1e iron4 Cr is -a(a.le of e6hi.itin* a 'aria.le Cr2G/Cr3G ratio in sla*4 de(endin* on the o6y*en (otential and .asi-ity In red,-in* sla* 4 Cr: is dominant )hereas in o6idi8in* 4 Cr2:3 is the ma/or s(e-ies i0e let ,s -onsidered as Cr2:30 3Cr2:35 G > C ? >KC:L G3Cr

7or 7e JCr C Melt

Hilty and Ma'eney

7or 7e JCr !i C Melt Hilty and Ma'eney

Here <-o ?002@atm
Tem 6cr.6c p 'K( '7e2Cr2 C( 1%E3 %& 6cr.6c '7e2Cr2C2Ni 12&

1&E3 !i-1el 20& in liF,id 2&@ iron has si*nifi-ant ;issol'ed 20E3 a-ti'ity >1B B1& infl,en-e of Car.on and :6y*en

Nhen -ar.on has .een remo'ed to ne-essary le'el4 the .ath is red,-ed .y 7e Si to re-o'er the Cr from sla*0 The heat is finished .y deo6idation .y 7e Si addition0 it also red,-es .a-1 )hate'er -hromi,m is in sla* at end3&E250 Alon* )ith 7e Si4 lime is added to (rod,-e a sla*0 Sla* formation and sla* metal rea-tion is fa-ilitated .y ar*on stir ,sed thro,*ho,t this (eriod0 Sla* )as not remo'ed ,ntil -hromi,m )as )on .a-1 in .ath0 It is also effe-ti'e in o.tainin* *ood s,l(h,r remo'al ,sin* ar*on stirrin* at end so far -har*e material )as OOOO

3irect stainless steel ma&ing
Nhere s-ra( and ferro alloy are e6(ensi'e or are not a'aila.le 4alternati'e (ro-ess ro,te ha'e .een de'elo(ed that ,se -hromi,m ore alon* )ith hot metal as -har*e0 In Ja(an se'eral s,-h installation are in ,se 4 the most )ell 1no)n of )hi-h is that MANASAMI ST##" C:R<:RATI:! 3SR MCB5

SR2KC8 process o direct SS ma&ing

Nitrogen pro4lem in stainless steel

P !itro*en is 1no)n for a*es to -a,se strain .rittleness in steel 0 That is the reason )hy it )as 1e(t .are minim,m for most steel 0its -reate serio,s (ro.lem in deformation d,rin* rollin*0 It$s a interstitial element and strain iron latti-e 0This )as the reason )hy .asi- Bessemer steel )ere not (referred for many a((li-ation0 Ar-elor Mittal

Conclusion
315 SS are )idely (rod,-ed .y #A7QA:; ro,te 325 In A:; 4 Ar is ,sed to dil,te the other *ases or

red,-e the (artial (ress,re of C: 335 Hi*h tem(erat,re (referred to o6idi8e only Car.on .,t not a -hromi,m 3>5 7e Si added to re-o'er the o6idi8ed -hromi,m from sla* and 1ill the molten .ath 3@5 Rse of "C 7e Cr and =:; are e6(ensi'e (ro-ess 3B5 Some time !itro*en is re(la-e for Ar and !i-1el as )ell