JOURNAL DE PHYSIQUE

Colloque C1, suppl6ment au n o 1, Tome 45, janvier 1984

page Cl-625

FERROMAGNETIC TRACES IN AUSTENITIC STAINLESS STEELS AT

X. Pieterman, A. Ketting and J. Ch. Geerse

4,2 K

Dept. f o r Applied Physics, D e l f t University of TechnoZogy, Lorentzweg 1, 2628 CJ D e l f t , The netherlands

Resume Dans c e t a r t i c l e , sont d e c r i t e s des mesures magnetiques q u i se r a p p o r t e n t m r s a c i e r s inoxydables de l a s e r i e ALSI 300 1 4,2 K. I 1 a 6 t 6 examine j u s q u ' i i quel p o i n t l e comportement magnetique des d i f f e r e n t $ types, 6 t a i t i n f l u e n c e p a r soudage ou p a r frequents r @ f r o i d i s s e m e n t s , j u s q u ' i i 4,2 K. De plus, l ' i n f l u e n c e de d i f f e r e n t e s a d d i t i o n s s u r l a s t a b i l i t e de l a s t r u c t u r e a u s t e n i t i q u e a e t 6 consideree. Des preparations examinees, une grande p a r t i e (303, 304, 310, 316L, 316Ti, 321) semblait montrer une c e r t a i n e forme de comportement ferro-magnetique, t a n d i s que seulement peu d ' a u t r e s (X6CrNi 1811,316LN) r e s t a i e n t compl6tement paramagnetiques 1 4,2 K. Abstract This paper describes magnetisation experiments on austeni t i c s t a i n l e s s s t e e l s o f A I S I 300 s e r i e s a t 4.2 K. The i n f l u e n c e o f welding and c y c l i c c o o l i n g on t h e i r magnetic behaviour was studied, as was t h e i n f l u e n c e o f t r a c e a d d i t i o n s f o r s t a b i l i z i n g t h e p r o p e r t i e s o f s t a i n l e s s s t e e l . A l a r g e number o f samples has been studied, most o f them showed ferro-magnetic t r a c e s a t 4.2 K (303, 304, 310, 316L, 316Ti, 321). Only a few remain f u l l y paramagnetic (X6CrNi 1811, 316LN) a t 4.2 K. INTRODUCTION The s t a b i l i t y o f a u s t e n i t i c s t a i n l e s s s t e e l s has been s t u d i e d e x t e n s i v e l y i n t h e pastl '2 '3 ' 4 ' 5 ' . I t i s w e l l known t h a t most o f them are unstable below room temp e r a t u r e f o r t h e t r a n s i t i o n i n t o t h e m a r t e n s i t i c phase. Because t h e a u s t e n i t i c phase i s paramagnetic and t h e m a r t e n s i t i c phase i s ferromagnetic, t h e magnetic c h a r a c t e r o f t h e s t e e l w i l l change. Whether such a t r a n s i t i o n occurs depends very c r i t i c a l l y on t h e chemical composition o f the s t e e l , so d i f f e r e n t heats o f t h e same type o f s t a i n l e s s steeT may show u n l i k e magnetic behaviourl. When using s t a i n l e s s s t e e l s i n t h e neighbourhood o f magnetic f i e l d s i t i s important t o know t h e i r magnetic behav i o u r , e s p e c i a l l y when h i g h homogeneities are r e q u i r e d . I n t h a t respect i t i s a l s o necessary t o know t h e i n f l u e n c e o f welding on t h e magnetic c h a r a c t e r o f t h e s t a i n l e s s s t e e l . I n t h i s paper maqnetisation measurements 303, 304, 304N, 310, a r e r e p o r t e d on welded and unwelded samples o f t h e types AISI 310S, 316, 3161, 316LN, 316Ti and 321 a t 4.2 K. PREPARATION O F THE SAMPLES The samples were machined o u t o f bars received from d i f f e r e n t manufacturers i n t o c y l i n d e r s o f 10 m m diameter and 10 m m long. For each type o f s t a i n l e s s s t e e l m were machined and bounded together by fusion-wela l s o two c y l i n d e r s o f 10 by 5 m ding. Welded and unwelded samples were machined o u t o f the same bar. Chemical anal y s i s of each specimen was c a r r i e d out; t h e r e s u l t s a r e l i s t e d i n t a b l e l. Out o f t h e 32 samples used i n t h i s study 22 were annealed a t 1 0 8 0 ~ fo ~r 90 minutes and quenched i n water. The magnetisation o f 3 samples was measured b e f o r e and a f t e r heat treatment. The amount o f ferromagnetism was reduced, b u t o n l y one o f them (316) was f u l l y paramagnetic a f t e r heat treatment, i n d i c a t i n g a pure a u s t e n i t i c s t r u c t u r e (see t a b l e 2 ) .

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19841127

C1-626

JOURNAL DE PHYSIQUE

Table 1. Chemical analysis o f the measured s t a i n l e s s s t e e l samples. (Compositions i n w t %) Alloyname

303 304 (a) 304(b) 304 N ' 310 310 S 316 (a) 316 (b) 316 ( c ) 316 L 316 LN 316 T i X6CrNi 1811 321 (a)
321 ( b )

Cr

Ni

Mn

Mo

Ti

Si

Cu

0.062 0.055 0.067 0.075 0.066 0.062 0.070 0.034 0.044 0.033 0.032 0.055 0.072 0.066 0.057

Table 2. Magnetic s u s c e p t i b i l i t y and s a t u r a t i o n magnetisation o f d i f f e r e n t specimens a f t e r f i r s t c o o l i n g a t 4.2 K A1 1oy name ~ond tii onX xo
X,

h a t (kA/m)

303 304 304 304 304 310 310 316 316 316 316 316 316 316

(a)

(b)
(cj N
S

AWQ A M AM

14.5 22.7 7.1

5.5 4.2 7.1

1.1 1.5 0

(a) (6) (cj (cj

L LN Ti

323 (a) 321 (a) 321 (b)

"AM = As machined f o~r 90 minutes, then water quenched AWQ = annealed a t 1 0 8 0 ~

EXPERIMENTAL PROCEDURE Measurements concerning the magnetic s u s c e p t i b i l i t y x = ( aM )T. have been made a t 4.2 K i n magnetic f i e l d s up t o 1 T. The specimens were moungd ~ n s i d e a sample holder t h a t f i t s i n an ac magnetometer surroundedby a superconducting magnet. The sample holder could be e a s i l y taken o u t o f the c r y o s t a t f o r quick changing the

sample. Cool-down time f o r t h e samples was t y p i c a l l y 2 minutes, they were h e l d a t l i q u i d helium temperature f o r about 15 minutes t o sweep the magnetic f i e l d t o 1 T and back and measure t h e magnetic s u s c e p t i b i l i t y . Afterwards t h e samples were a l lowed t o warm up t o room temperature i n a i r . C y c l i c c o o l i n g e f f e c t s were s t u d i e d on 13 samples by c o o l i n g them down once every day d u r i n g a p e r i o d o f 14 days. Holding t i m e i n l i q u i d helium was 15 minutes each time. RESULTS N o n - l i n e a r i t y o f t h e magnetisation curves i n d i c a t e s ferromagnetic t r a c e s i n t h e s t a i n l e s s s t e e l . I n t h e case o f t h e unwelded samples t h i s i s caused by t h e f o r mation o f a' martensite. The s a t u r a t i o n magnetisation Msat o f t h e ferromagnetic p a r t i n d i c a t e s t h e amount o f a' m a r t e n s i t e . I n t h e case o f t h e welded samples, f e r romagnetism i s caused by m a r t e n s i t e formation on c o o l i n g and welding by 6 - f e r r i t e and carbide formation induced by t h e welding process. Ferromagnetism induced by welding o n l y can be found by s u b s t r a c t i n g t h e measured Msat values (Msatw - Msatu i n t a b l e 3). Table 3. Magnetic s u s c e p t i b i l i t y and s a t u r a t i o n magnetisation o f d i f f e r e n t specimens a f t e r welding a t 4.2 K. A1 l o y name Condition

xo
25.1 47.3 22.2 93.2 8.2 246 92.0 14.5 16.7 13.0 45.6 11.8 31.0 9.9 25.0 38.7

X ,
7.4 6.4 7.2 9.6 6.8 37.0 20.0 9.7 16.7 13.0 12.3 11.8 12.9 9.9 15.1 14.9

Msat (kA/m)

Msatw- Msatu (kA/m)

~ t a b iiltyX on welding

303 304 304 304 304 310 310 316 316 316 316 316 316

(a) (b) (c) N

AM
A M A M AWQ A W Q A M A M A W Q A W Q AWQ A W Q A W Q AWQ

S (a) (b) (c) L LN Ti X6CrNi 1811 321 ( a ) 321 (b)

1.7 3.3 1.3 6.1 0.1 22.0 14.2 0.3 0 0 2.2 0 1.6 0 2.4 2.5

0.6 1.8 1.3 -5.5 0 1.2 4.4 0.3 0 0 -0.2 0 -0.3 0 -2.9 -0.2

+ + +

+ +++ +++ ++ + ++++ ++++ ++ ++++ ++ ++++

+ ++

++

+++ ++++

= poor = reasonable

= good
= excel l e n t

FERROMAGNETIC TRACES AT FIRST COOLING

4.2 K are l i s t e d i n t a b l e 2; x0 i s the magnetic s u s c e p t i b i l i t y a t zero a p p l i e d

The r e s u l t s o f t h e magnetisation o f t h e unwelded samples on f i r s t c o o l i n g t o

f i e l d , X , a t maximum f i e l d where t h e ferromagnetic p a r t i s s a t u r a t e d and M s a t i s t h e s a t u r a t i o n magnetisation. Out o f 16 measured specimens o n l y 6 showed f u l l y paramagn e t i c behaviour on f i r s t cooling. Important i s t h a t a l l o f t h e untraced 316 type specimens remain f u l l y a u s t e n i t i c , where o n l y one o f t h e 304 samples showed no ferromagnetism. Also t h e 316LN specimen and t h e s p e c i a l composite X6CrNil811 r e mained a u s t e n i t i c . The 304N type shows a s l i g h t l y n o n - l i n e a r behaviour, although i t i s r e p o r t e d t o be f u l l y paramagnetic i n t h e The r e s u l t s i n d i c a t e

'21-628

JOURNAL DE PHYSIQUE

t h a t i n t h e case of t h e 304 type t h e o c c u r r i n g o f y - a' t r a n s f o r m a t i o n i s more c r i t i c a l l y dependent o f t h e chemical composition than i n t h e case o f t h e 316 type o f s t a i n l e s s s t e e l . Comparing t h e chemical analyses w i t h t h e magnetic behaviour o f t h e 304 specimens one may conclude t h a t a low carbon t o g e t h e r w i t h a h i g h chromium cont e n t enhance m a r t e n s i t e formation. Also t h e i n f l u e n c e o f t h e a u s t e n i t e s t a b i l i z i n g Mn a d d i t i o n i s important as i s seen i n t h e case o f sample 304(c) w i t h a h i g h value f o r MSat and a low Mn content. FERROMAGNETIC TRACES INDUCED BY WELDING Table 3 shows t h e r e s u l t s o f t h e measurements o f t h e welded samples. The chemic a l composition i s t h e same as f o r t h e unwelded samples. A f t e r welding t h e number o f specimens t h a t remained f u l l y paramagnetic decreased t o f o u r (316(b), 316(c), X6CrNi 1811 and 316LN). The f i r s t t h r e e showed a s l i g h t decrease i n magnetic suscept i b i l i t y (resp. 5, 4 and 2%) and o n l y t h e 316 LN type o f s t a i n l e s s s t e e l showed no d i f f e r e n c e whatsoever. A l a r g e increase of t h e ferromagnetic p a r t was found f o r t h e samples 303 and 304 whereas sample 304(c) showed a l a r g e decrease o f t h e ferromagnetic part. T h i s i n d i c a t e s again t h e r a t h e r u n s t a b l e c h a r a c t e r o f these types o f s t a i n l e s s s t e e l and t h e l a r g e dependence o f t h e magnetic c h a r a c t e r on thermal h i s t o r y and chemical composition. Only t h e 304N type may be regarded as f a i r l y s t a b l e w i t h and w i t h o u t welding. With one exception (303) a l l o f t h e annealed samples showed decreasing magnetisation a f t e r welding. Only i n one case (304(c)) o f t h e "as-machined" samples, i n d i c a t e d i n t a b l e 3 by A M ("as-machined"), showed decreasing magnetisation. Table 3 a l s o gives t h e s t a b i l i t y on welding o f t h e d i f f e r e n t types o f s t a i n l e s s s t e e l w i t h r e s p e c t t o t h e changes i n magnetisation. The Mo s t a b i 1i s e d types 316 have excel l e n t p r o p e r t i e s i n t h i s r e s p e c t except f o r sample 316(a) which may g i v e b e t t e r r e s u l t s when annealed. The low carbon s t e e l 316L i s s t a b l e on welding b u t i t showed ferromagnetism on f i r s t cooling. S u r p r i s i n g l y t h e X6CrNi 1811 sample w i t h o u t Mo a d d i t i o n showed very good r e s u l t s . It remains f u l l y paramagnetic and has e x c e l l e n t s t a b i l i t y . The so c a l l e d weldable s t e e l s w i t h T i a d d i t i o n o f t h e types321 and 316Ti showed l e s s s t a b i l i t y than t h e 316 and 316LN types. Even a f t e r annealing they showed ferromagnet i c t r a c e s and must be regarded as u n s t a b l e as was s t a t e d i n r e f . 7 . Fig. 1 shows some t y p i c a l l y magnetisation curves f o r welded and unwelded specimens. FERROMAGNETIC TRACES O N CYCLIC COOLING C y c l i c c o o l i n g e f f e c t s have been s t u d i e d on 13 d i f f e r e n t specimens: 304(d), 304N, 310, 310S, 316(a), 316(b), 316(c), 316L, 316LN, 316Ti, X6CrNi 1811, 321(a), 321(b). O f t h e measured specimens f o u r showed i n c r e a s i n g ferromagnetism on c y c l i c c o o l i n g namely: 304(d), 304N, 310 and 321(b). The r e s u l t s a r e shown i n f i g u r e 2. The t h r e e types o f s t a i n l e s s s t e e l specimens showed d i f f e r e n t behaviour on c y c l i c cooling. Both 304 types showed no e f f e c t on t h e f i r s t f o u r cooldown runs t o 4.2 K. A f t e r t h a t a sharp r i s e i n M at was detected. 304 was r e p o r t e d unstable1, b u t c y c l i c c o o l i n g e f f e c t s on 304N sampfes are n o t published as f a r as we know. I n r e f . 2, 4, 6 and 8 304N was r e p o r t e d s t a b l e . Again we must conclude t h a t t h e magnetic character o f these s t e e l s i s u n p r e d i c t a b l e because o f t h e wide commercial composition l i m i t s . Sample 310 shows a s l i g h t increase o f ferromagnetism from t h e f i r s t c o o l i n g c y c l e onwards which remains t h e same a f t e r 10 cycles. The e f f e c t i s r a t h e r small, o n l y a 2% increase o f Msat a f t e r 10 cycles. I n r e f . 2 i t was r e p o r t e d s t a b l e . Sample 321(b) shows a l a r g e increase o f M s a t between the f i r s t and t h e second cooldown and a s l i g h t f u r t h e r increase i n t h e n e x t 9 cooldown runs. This e f f e c t was a l s o r e p o r t e d i n r e f . 2. The o t h e r specimen o f t h i s type o f s t e e l (321(a)) showed no e f f e c t s on c y c l i c c o o l i n g as was r e p o r t e d i n r e f . 1. The d i f f e r e n c e between these two samples c o u l d be explained by l o o k i n g a t t h e chemical composition: sample 321(a) c o n t a i n s t w i c e as much of t h e a u s t e n i t e s t a b i l i s i n g Mn as sample 321(b). T h i s was e x a c t l y t h e case w i t h t h e samples o f L a r b a l e s t i e r and King2 (Mn0.77, u n s t a b l e ) and o f Reed and M i k e s e l l ' (Mn2.0, s t a b l e ) .

Fig. 1 - Magnetisation curves of different s t a i n l e s s steel samples. Straight line before welding, dotted l i n e - a f t e r welding.

Cl-630

JOURNAL DE PHYSIQUE

Fig. 2 - Magnetisation of different specimens as function of the number of cooling cycles N between room temperature and 4.2 K. Table 4. Summary of r e s u l t s A 1 1oy name
303 304 ( a ) 304 (b) 304 ( c ) 304N 310 310s 316 ( a ) 316 (b) 316 ( c ) 316L 316LN 316Ti X6CrNi 1811 321 ( a ) 321 (b)

ferromagnetic traces on f i r s t cooling on welding on c y c l s cooling

+ + + + + + + -

+ +

+ + t + + + + + +

+ +

x x
f

= not detected x = nbt tested

= detected

CONCLUSIONS Table 4 summarizes t h e r e s u l t s o f t h e magnetisation measurements on 16 d i f f e r e n t types o f s t a i n l e s s s t e e l . Four samples remained paramagnetic under a l l circumstances: 316(b), 316(c), 316LN and X6CrNi 1811. These types may be regarded as s t a b l e a u s t e n i t i c s t a i n l e s s s t e e l s . Sample 316(a) showed some ferromagnetism on welding probably due t o t h e low M o content. I n t h e case o f t h e 303, 304 and 321 samples we can conclude t h a t one cannot be sure about t h e i r magnetic c h a r a c t e r i n advance. The knowledge o f t h e chemical composition c o u l d be h e l p f u l t o p r e d i c t whether ferromagnetic t r a c e s w i l l occur, b u t i n general when magnetic behaviour i s c r i t i c a l one should n o t use these types o f s t a i n l e s s s t e e l unless exact magnetisation measurements has been done. I n t h e case o f t h e 310 specimens a b s o l u t e magnetisation i s f a i r l y l a r g e . There i s a p o s s i b i l i t y o f a ferromagnetic t r a n s i t i o : i n t h e a u s t e n i t i c phase caused by t h e l a r g e amount o f Ni i n these types o f s t e e l . That leaves o n l y t h e 316LN type o f s t e e l t o be p e r f e c t l y s t a b l e (no evidence o f t h e c o n t r a r y i s known i n t h e l i t e r a t u r e ) and t h e t y p e X6CrNi 1811, o f which we a r e n o t aware o f any r e s u l t s published before. ACKNOWLEDGEMENT The authors wish t o thank P r o f . H. Postma f o r h i s advice and encouragement. They a r e a l s o g r a t e f u l t o Mr. G.J. Maanenschijn and M r . P.F. C o l i j n o f t h e Metall u r g i c a l Department f o r analyzing t h e samples and h e l p f u l discussions. The t e c h n i c a l assistance o f Mr. W. den Braver a t t h e p r e p a r a t i o n o f the experimental set-up i s g r a t e f u l l y acknowledged. REFERENCES

1 . 2. 3. 4. 5. 6. 7. 8.

REED R.P. and MIKESELL R.P., Adv. Cryog. Eng. 4 (1960) 84. LARBALESTIER D.C. and KING H.W., Cryogenics 13-(1972) 160. WARNES L.A.A. and KING H.W., Cryogenics 16 ( m 7 6 ) 473. COLLINGS E.W., Adv. Cryog. Eng. 26 (1979737. WARNES L.A.A. and KING H.W., C r y G e n i c s 21 (1982) 729. (197 9) 521. COLLINGS E.W. and HART S.C., Cryogenics KING H.W.. CIM B u l l e t i n J u l y 1981. GEYARI C.; Vacuum 26 (1976) 587.