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W. A. KRIVSKY
Dr. Krivsky has served on several technical committees of AIME and is a past
chairman of the Extractive Metallurgy Division. He has also served as a director of
TMS and is currently an AIME director. In 1959 he was recipient of the Extractive
Metallurgy Division's Gold Medal,jointly with Dr. R. Schuhmann, for their contribution on the thermodynamics of copper smelting. In 1965 he edited the book
High TemperatureRefractory Metals based upon an international symposium
which he organized and chaired for the AIME.
The 1973 Extractive Metallurgy Division Lecture was delivered on Feb, 28 at
the 102nd TMS-AIME Annual Meeting in Chicago.
V O L U M E 4, J U N E 1 9 7 3 - 1 4 3 9
TODAY
ORIGIN O F T H E P R O C E S S
How did it all begin ? What was the o r i g i n of the i n v e n t i o n and how was it d e v e l o p e d into the c o m m e r c i a l
p r a c t i c e we h a v e today ?
It all s t a r t e d in 1954 at the M e t a l s R e s e a r c h L a b o r a t o r i e s of the Union C a r b i d e C o r p o r a t i o n in N i a g a r a
F a l l s , New York, in quite an innocent m a n n e r and w i t h out s p e c i f i c a l l y a t t e m p t i n g to d e v e l o p a new s t e e l m a k trig p r o c e s s . J u s t p r i o r to that t i m e , R i c h a r d s o n in
England had p u b l i s h e d a t h e r m o d y n a m i c study of the
r e l a t i o n s h i p of c h r o m i u m to c a r b o n in s t a i n l e s s s t e e l
r e f i n i n g in which he had c l a s s i c a l l y e q u i l i b r a t e d c a r b o n
m o n o x i d e - c a r b o n dioxide gas m i x t u r e s with F e - C r - C
m e l t s . His r e s u l t s w e r e s o m e w h a t d i f f e r e n t than t h o s e
of Hllty and C r a f t s p u b l i s h e d e a r l i e r . The e x p e r i m e n t a l
m e t h o d of Hilty and C r a f t s was s u b s t a n t i a l l y d i f f e r e n t
f r o m that of R i c h a r d s o n in that t h e y had blown s m a l l
induction f u r n a c e h e a t s of F e - C r - C with oxygen, a t t e m p t i n g to e s t a b l i s h e q u i l i b r i u m v a l u e s for c h r o m i u m
and c a r b o n by a p p r o a c h i n g s u c h v a l u e s f r o m both high
and low c a r b o n c o n t e n t s . The p r e s e n t a u t h o r s e t out to
r e s o l v e the d i f f e r e n c e in the two s t u d i e s by extending
the r a n g e of C r - C r e l a t i o n s h i p studied following the
g e n e r a l e x p e r i m e n t a l m e t h o d of Hilty and C r a f t s . The
i n i t i a l w o r k w a s done in a 100-pound induction f u r n a c e ;
and it b e c a m e r a p i d l y e v i d e n t that, in a t t e m p t i n g to e s t a b l i s h e q u i l i b r i u m Cr-42 r e l a t i o n s h i p s , i t was e s s e n t i a l l y
i m p o s s i b l e to a c h i e v e the i s o t h e r m a l conditions n e c e s s a r y b e c a u s e of the highly e x o t h e r m i c n a t u r e of the C r - O
METALLURGICAL TRANSACTIONS
Conventional
A-O2
Meltcharge in electricfurnace
a) 18 pct Cr chargedevenfor ELC grades
b) deslagmeltedchargetransfer charge;to
AODvessel
Blowwith oxygen-argonmixture;end point
3100~
17 pet Cr
0.03 pet C
Recover0.75 pct Cr fromslag.Pure argon
injection
Nolowcarbon FeCraddition necessary
Final Compositon:
Cr-18.5 pct
C-0.OI pet
VOLUME 4, JUNE 1973-1441
0.5-
Conventional
Practice
Argon-Oxygen
Practice
0.2
--
[ Oxygen Blow
[)
0.1
~rgon-Oxygen
/
Blow
@
0.05
i+>. . . . . . . . . .
I
0.02
0.01
--
0.005
\-"
,--
/\
Finish-Using Major
Additions of Fe Cr Si,
LC-Fe Cr, etc
Finish-Using
Minor Additions
of Fe Cr Si, Fe Si, etc.
12
16
20
Chromium %
Fig. 6--Conventional vs Argon-oxygen p r a c t i c e for 302L.
w e r e n e a r l y p r o h i b i t i v e b e c a u s e of the e f f e c t of the
high f i n i s h i n g t e m p e r a t u r e s on r e f r a c t o r y life a s well
a s the p o o r r e p r o d u c i b i l i t y of the c o n v e n t i o n a l p r o c e s s . The a r g o n dilution p r i n c i p l e a p p e a r e d to a f f o r d
METALLURGICAL TRANSACTIONS
Table III.
Carbon Content as a Function of Argon-Oxygen Ratio v$ Conventional Practice
Pco Atm
Reduction in
Carbon Level, pct
33-~
50
-~
66 2
-~
8o
90
8
18
Union C a r b i d e , not b e i n g a s t a i n l e s s s t e e l p r o d u c e r ,
had gone about a s f a r a s it could go a l o n e in the s c a l e up e f f o r t s . It o b v i o u s l y n e e d e d a p a r t n e r with l a r g e r
f u r n a c e s in o r d e r to b r i n g the p r o c e s s to full c o m m e r c i a l s c a l e . A long s e a r c h of a l l the s t a i n l e s s s t e e l p r o d u c e r s followed, with v e r y d i s c o u r a g i n g r e s u l t s in g e n eral. For various reasons, nearly every company dec l i n e d to p a r t i c i p a t e in the f u r t h e r d e v e l o p m e n t until
the J o s l y n S t a i n l e s s Steel C o m p a n y was a p p r o a c h e d .
H e r e , in s p i t e of the f a c t that t h e y w e r e one of the
s m a l l e r p r o d u c e r s without the t e c h n i c a l and f i n a n c i a l
r e s e r v e s of s o m e of t h e i r l a r g e r c o m p e t i t o r s , t h e y
n e v e r t h e l e s s had the c o u r a g e and f o r e s i g h t to p r o c e e d .
In 1960 Union C a r b i d e and J o s l y n s i g n e d a j o i n t d e v e l opment agreement.
The f i r s t t e s t s c o n d u c t e d at J o s l y n on a 15 ton s c a l e
t u r n e d out to b e n e a r l y a b s o l u t e , d i s m a l f a i l u r e s . A l though a g r e a t d e a l of a t t e n t i o n had b e e n p a i d to the
l a n c e p r o b l e m and v a r i o u s m e t h o d s , including the u s e
of t h r e e f i r e c l a y - s l e e v e d l a n c e s p o s i t i o n e d above the
b a t h , w e r e t r i e d , no s u c c e s s f u l h e a t s w e r e p r o d u c e d .
V e r y c a r e f u l and d e t a i l e d a n a l y s i s of the r e s u l t s i n d i c a t e d that while l o c a l a c t i o n of the a r g o n dilution p r i n c i p l e n e a r the point of i n j e c t i o n was e f f e c t i v e , the net
e f f e c t on the e n t i r e b a t h , a f t e r it had h o m o g e n i z e d f o l lowing the blow , w a s i n c o n s e q u e n t i a l . L a r g e s c a l e
t e s t i n g was r e g r e t f u l l y a b a n d o n e d but w o r k w a s c o n t i n u e d on a l a b o r a t o r y s c a l e . This w o r k a g a i n c l e a r l y
i n d i c a t e d the f e a s i b i l i t y of the p r o c e s s if the a r g o n
could be d i s t r i b u t e d t h r o u g h o u t the e n t i r e bath. The
p r o c e s s n e v e r f a i l e d to p e r f o r m under such c i r c u m s t a n c e s . C o n v e r s e l y , w h e n e v e r the b a t h d i a m e t e r was
l a r g e r e l a t i v e to s u r f a c e i n j e c t i o n d e v i c e s , no d i s c e r n ible b e n e f i t was a c h i e v e d in the b a t h a s a whole.
R E C O V E R Y FROM F A I L U R E
A r m e d with t h i s m o r e c l e a r u n d e r s t a n d i n g , Union
C a r b i d e and J o s l y n m a d e the h i s t o r i c d e c i s i o n to b u i l d
a r e f i n i n g v e s s e l a p a r t f r o m the e l e c t r i c a r c f u r n a c e .
T h i s f i r s t such v e s s e l w a s only -~ ton in c a p a c i t y and
p r o v i d e d f o r the top blowing of oxygen and the b o t t o m
i n j e c t i o n of a r g o n t h r o u g h a t u y e r e . The r e s u l t s w e r e
d r a m a t i c a l l y f a v o r a b l e and s u p p o r t e d a l l the l a b o r a t o r y
s c a l e w o r k p r e v i o u s l y done.
H o w e v e r , the i d e a of a p p l y i n g the a r g o n d i l u t i o n p r i n c i p l e d i r e c t l y in the e l e c t r i c f u r n a c e d i e d v e r y s l o w l y .
T h e r e was obvious r e l u c t a n c e to d e v e l o p a p r o c e s s
that would c r e a t e a n o t h e r s t e p in the m a n u f a c t u r i n g
p r o c e s s and t h a t would r e q u i r e an a d d i t i o n a l c a p i t a l
i n v e s t m e n t . What was not r e a l i z e d at t h i s p o i n t in
t i m e , w a s that the s e p a r a t e r e f i n i n g v e s s e l would
double the s t e e l output of a given f u r n a c e . Since its
c o s t w a s o n l y a s m a l l f r a c t i o n of the c o s t of an a d d i t i o n a l e l e c t r i c f u r n a c e , it r e p r e s e n t e d a v e r y i n e x p e n s i v e m e a n s of i n c r e a s i n g s t e e l m a k i n g c a p a c i t y . N e v e r t h e l e s s , f o r t y - f i v e a d d i t i o n a l 15-ton h e a t s w e r e t r i e d in
the a r c f u r n a c e , which, in s p i t e of v a r i o u s c o n f i g u r a t i o n s of l a n c e s , t o t a l l y f a i l e d to give a n y b e n e f i c i a l r e s u l t s c o m p a r e d to the -~ ton s e p a r a t e v e s s e l .
As a r e s u l t of t h e s e e f f o r t s , the two c o m p a n i e s p r o c e e d e d with the d e s i g n of a 1 5 - t o n s e p a r a t e r e f i n i n g
v e s s e l . A f t e r much e x p e r i m e n t a t i o n with top and b o t V O L U M E 4, J U N E 1 9 7 3 - 1 4 4 3
Table IV. Log of First Complete Stainless AOD Heat October 24, 1967
304L
Time, min
Pet C
Pct Cr
ppm 02
B/4tap
B/402
~ep 1
~ep 2
argon
addns.
product
-4
6
28
46
51
58
-
0.290
0.259
0.084
0.033
0.027
0.021
0.008
18.08
18.02
16.99
16.46
16.46
17.60
18.62
600
230
560
800
660
390
170
3140
2990
3160
3130
3100
2980
-
Company
Startup Date
Vessel
Capacity
Tons
1/71
35
Baldwin-l.Jma-Hamihon Corp.
Standard Steel Division
Burnham, Pennsylvania
8171
18
Mid. 1973
25
1170
1172
15
3/72
100
11/70
50
Eleetralloy Corporation
Off City, Pennsylvania
9/70
17
10/71
38
10/71
20
12/71
70
4/68
17
12171
100
Company
It must be r e m e m b e r e d that Union Carbide Corporation is not a stainless steel producer and the outstanding success at Joslyn needed to be repeated m a n y
m o r e times before the project would be a commercial
s u c c e s s for Union Carbide. P r a c t i c a l l y e v e r y major
s t a i n l e s s s t e e l p r o d u c e r in the world was contacted.
With the cooperation of Joslyn, d e m o n s t r a t i o n s were
a r r a n g e d for v a r i o u s companies at F o r t Wayne. Savings calculations were made for e v e r y potential l i c e n see under l i t e r a l l y thousands of local conditions and
p r o c e s s a l t e r n a t i v e s . Questions of f u r t h e r s c a l e - u p
and product quality had to be answered. P r o s p e c t s
were enabled to take J o s l y n - p r o d u c e d AOD ingots,
finish them in their own m i l l s , evaluate, and test
m a r k e t them. In c e r t a i n c a s e s Union Carbide even
a r r a n g e d to have the 15-ton t e s t v e s s e l at Joslyn
shipped to v a r i o u s p r o s p e c t s so that they might a c tually c a r r y out t h e i r own t e s t s . In spite of local diff i c u l t i e s in accommodating the v e s s e l , this p r o g r a m
was highly developed and e x t r e m e l y s u c c e s s f u l in
convincing p r o s p e c t s to obtain l i c e n s e s to the p r o c e s s .
The second l i c e n s e e to the p r o c e s s in the United States
was E l e c t r a l l o y in September of 1970; the f i r s t foreign
l i c e n s e e was Illsa Viola in Italy in July of 1970. The
final t r i b u t e s to Llnde and Union Carbide m a r k e t i n g
efforts may be seen in Table VI and Table VII which
r e s p e c t i v e l y l i s t s U. S. and foreign l i c e n s e e s . During
1973 Union Carbide expects 50 pct of the s t a i n l e s s
Startup Date
Vessel
Capacity
Tous
6/73
60
10173
18
11/71
60
7/72
15
1175
70
7/70
22
3/71
7/72
75
11/71
55
10172
7173
14
10
11171
9172
25
10/71
8172
60
Boschgotthardshutte
Siegen, W. Germany
British Steel Corp./Panteg Works
Pontypool, Wales, U. K.
British Steel Corp./Stuckshridge Works
Stucksbridge, U. K.
FIAT, Sp. A.
Torino, Italy
llssa Viola
Pont St. Martin, Italy
IMI Alloy Steels Ltd.
Somercotes, U. K.
Nippon Metal Industry Co.
Kinuura, Japan
Temi/Fmisider Group
Temi, Italy
VOLUME 4, JUNE 1 9 7 3 - 1 4 4 5
LESSONS F R O M THIS D E V E L O P M E N T
It is a g r e a t p l e a s u r e to able to recount the long and
arduous saga of an u l t i m a t e l y overwhelming s u c c e s s
s t o r y , e s p e c i a l l y when one has had a p a r t in it. This,
however, is not the main p u r p o s e ; f a r m o r e important
at this point is what we can l e a r n f r o m this e x p e r i e n c e
for our future mutual benefit. It is b e l i e v e d that there
a r e many l e s s o n s to be l e a r n e d h e r e concerning t e c h nical innovation which affect many c l a s s e s of individuals.
F o r the Individual R e s e a r c h e r
1) The l e s s o n taught h e r e is that of the e x t r e m e i m p o r t a n c e of looking for the unexpected or the unusual
in any r e s e a r c h work and the total acceptance of the
r e s e a r c h data. This may sound e l e m e n t a r y but it is
not always e a s y to do as a young, unknown r e s e a r c h e r
when faced with apparent contradictions with the published word of f a r m o r e well-known and r e s p e c t e d inv e s t i g a t o r s . In this case, the m a r k e d l y different r e sults obtained in the v e r y f i r s t argon t e s t s f r o m those
of the e a r l y Hilty and Crafts and Richardson studies
could have been a s c r i b e d to some m y s t e r i o u s and unknown e x p e r i m e n t a l e r r o r and the total development
could have been lost right at that point.
2) All unexpected r e s u l t s can be understood ultim a t e l y in t e r m s of b a s i c t h e o r y if a sufficient effort
is made. This e x t r e m e l y important step is highly p r o ductive of inventions and must be thoroughly pursued.
In this p a r t i c u l a r case, going back to fundamental
p h y s i c a l c h e m i s t r y led to a highly i m p o r t a n t new p r o c e s s which would have not been r e a c h e d had not this
step been c o m p l e t e l y executed.
3) R e g a r d l e s s of the scientific nature of r e s e a r c h
work, the r e s e a r c h e r must s t r i v e to understand the
p r a c t i c a l and c o m m e r c i a l environment of the s y s t e m
he is studying. In the p r e s e n t case it was not the o r t g 1446-VOLUME 4, JUNE 1973
METALLURGICAL TRANSACTIONS
VOLUME 4, JUNE 1 9 7 3 - 1 4 4 7