BR98E1515

• IMHUI miii 111 nni uiin un mil inu um tin nil

EFFECTS OF CARBON, CHROMIUM AND

MOLYBDENUM CONTENTS ON
SOLIDIFICATION AND MICROSTRUCTURE
OF 15 OR 20% Cr V/HITE CAST IRONS

A. Sinatora
H. Goldenstein
P. R. Mei
E. Albertin
R. Fuoco
C. L. Mariotto

Sao Paulo, 1992

I
29-42
 We regret that
some of the pages
in this report may
not be up to the
proper legibility
standards, even
though the best
possible copy was
used for scanning
i •... iito de Pesquisas Tecnológicas do Estado de S5o Paulo S.A. - IPT
ò;oao'e Universitária Armando de Salles Oliveira - Bulantã - CEP 05508 - S3o Paulo-SP
Caixa Postal 7141 - CEP 01051 - Endereço Telegrafico TECNINST - Telex (11) 80934 e
(11) 83144 INPT BR - Telefax (011) 869-3353 - Telefone (011) 268-2211

DivisSo de Metalurgia
Coordenador: Cláudio Luiz Mariotto

Trabalho publicado nos Anais do 55g International Foundry Congress, Moscow: CIATF, 1988. p.4.1 -4.17.

A série "Comunicação Técnica" compreende trabalhos elaborados por técnicos do IPT, apresentados em eventos ou
publicados em revistas especializadas, sendo seu conteúdo de responsabilidade da respectiva área técnica.

Publicação IPT 1929

 ABSTRACT

S o l i d i f i c a t i o n e x p e r i m e n t s w e r e p e r f o r m e d o n 3 0 m m d i a m e t e r test
p i e c e s of w h i t e i r o n s c o n t a i n i n g 1 5 or 2 0 % c h r o m i u m a n d 2,3 , 3,0
a n d 3 , 6 % c a r b o n , w i t h a d d i t i o n s o f z e r o , 1 , 5 o r 2 , 5 % m o 1 y b d e n u m for
each carbon content.
M e a s u r e m e n t s w e r e made o f : a u s t e n i t e and. e u t e c t i c temperature
a r r e s t s ; n u m b e r o f e u t e c t i c . c a r b i d e p a r t i c l e s r e l a t i v e to total v o L -
u m e a n d to e u t e c t i c v o l u m e ; v o l u m e f r a c t i o n o f p r i m a r y austenito.
It w a s o b s e r v e d t h a t i n c r e a s i n g c a r b o n c o n t e n t s c a u s e d lower
a u s t e n i t e a n d e u t e c t i c f o r m a t i o n t e m p e r a t u r e a r r e s t s , reduced number
o f c a r b i d e p a r t i c l e s i n e u t e c t i c v o l u m e a n d s m a l l e r v o l u m e fraction
of p r i m a r y a u s t e n i t e .
T h e a d d i t i o n o f m o l y b d e n u m l e d to l o w e r a u s t e n i t e a n d e u t e c t i c
f o r m a t i o n t e m p e r a t u r e a r r e s t s , l e s s c a r b i d e p a r t i c l e s in t o t a l a n d
in e u t e c t i c v o l u m e , and l a r g e r v o l u m e f r a c t i o n of p r i m a r y austenite.
A s c o m p a r e d to 1 5 % c h r o m i u m a l l o y s , t h e 2 0 % c h r o m i u m alloys
showed higher eutectic temperature arrests, more carbide particles
b o t h in the t o t a l v o l u m e and in the e u t e c t i c v o l u m e , and smaller
v o l u m e f r a c t i o n of p r i m a r y a u s t e n i t e .

F i g u r e s 7 , 8 and 9 s u m m a r i z e the c o m b i n e d e f f e c t s of carbon,chro-

m i u m and m o l y b d e n u m o b s e r v e d . The r e s u l t s for 2 , 5 % Mo a d d i t i o n a r e
o m i t t e d in f i g u r e s 8 and 9 b e c a u s e they do not d i f f e r significantly
from those o b t a i n e d with 1,5% Mo a d d i t i o n .

F i g u r e 7 s h o w s h o w c h e m i c a l c o m p o s i t i o n i n f l u e n c e s a u s t e n i t e and
e u t e c t i c f o r m a t i o n t e m p e r a t u r e a r r e s t s ( T a m e a s u r e m e n t s r e l a t i v e to
1 , 5 % M o a d d i t i o n s d o n o t s h o w u p i n f i g u r e 7 ) . It m a y b e clearly
s e e n h o w c a r b o n and m o l y b d e n u m l o w e r the e u t e c t i c a r r e s t , while

chromium raises it.

F i g u r e 8 s h o w s h o w t h e a u s t e n i t e v o l u m e f r a c t i o n is d e c r e a s e d
by increasing carbon and/or chromium contents, and/or suppressing
mo 1ybd enum.

F i n a l l y , f i g u r e 9 d e p i c t s the i n f l u e n c e of chemical composition

on the n u m b e r of c a r b i d e p a r t i c l e s .
7 • ln.Oioduct.lon
T h e s o l i d i f i c a t i o n s e q u e n c e a n d m i c r o s t r u c L u r e of h i g h c h r o m i u m
white cast irons are dependent on chemical composition. Chromium
and carbon c o n t e n t s are factors which d e t e r m i n e the actual amount
of p r i m a r y a u s t c n i t e on .solidification, as w e l l as the n a t u r e of
the eutectic carbide formed (M3C or H 7 C 3 ) .

A c c o r d i n g to M a r a t r a y a n d N a n o t (1) t h e a m o u n t of primary
a u s t e n i t e f o r m e d at the s o l i d i f i c a t i o n d e t e r m i n e s the m i c r o s t r u c -
t u r e o f t h e e u t e c t i c . F o r t h e s e a u t h o r s , if t h e v o l u m e fraction o f
p r i m a r y a u s t e n i t e is l a r g e , t h e n t h e c a r b i d e t e n d s to " s e g r e g a t e "
a l o n g the g r a i n b o u n d a r i e s . S h o u l d the v o l u m e t r i c f r a c t i o n of c a r
b i d e s reach as m u c h as 20 or 3 0 % , then the m o r p h o l o g y of th^e
e u t e c t i c c o u l d be d e s c r i b e d as e u t e c t i c cells or c o l o n i e s . A third
k i n d of m o r p h o l o g y is d e s c r i b e d by M a r a t r a y for alloys whose
a u s t e n i t e d o e s n o t r e g u l a t e e u t e c t i c f o r m a t i o n , a s o c c u r s in a l l o y s
w i t h n e a r - e u t e c t i c c o m p o s i t i o n s . T h e s e a r e s a i d to exhibit lamellar
structures (1).

By r e m o v i n g t h e a u s t e n i t e w i t h a d e e p e t c h , P o w e l l ( 2 ) was a b l e
to o b s e r v e t h e e u t e c t i c c a r b i d e s t r u c t u r e s in a s c a n n i n g electron
m i c r o s c o p e . T h e c a r b i d e w a s s h o w n to b e i n t e r c o n n e c t e d within e a c h
eutectic cell, intermingling w i t h a u s t e n i t e , m u c h in the same
w a y as s i l i c o n a p p e a r s in t h e e u t e c t i c of m o d i f i e d A l - S i a l l o y s .

M a t s u b a r a ( 3 ) f o u n d o u t t h a t to a r i s e i n c h r o m i u m content f r o m
15 to 3 0 % c o r r e s p o n d e d a d e c r e a s e in e u t e c t i c c e l l d i a m e t e r a n d ,
at t h e s a m e t i m e , s m a l l e r i n t e r - c a r b i d e s p a c i n g s at t h e e d g e of
the e u t e c t i c c e l l . T h e s e t w o e f f e c t s w e r e a s c r i b e d to the reduc-
tion of the e u t e c t i c s o l i d i f i c a t i o n r a n g e .

A l t h o u g h t h e e f f e c t of c a r b o n is n o t d i s c u s s e d b y Matsubara ( 3 )
i t m a y b e i n f e r r e d f r o m h i s e x p e r i m e n t a l r e s u l t s that h i g h e r c a r b o n
c o n t e n t s p r o m o t e the e n l a r g m e n t of both the e u t e c t i c c o l o n i e s d i -
ameter and the i n t e r - c a r b i d e s s p a c i n g at cell e d g e .

Other authors found out that the larger the cooling r a t e , the
finer the eutectic morphology ( 4 ) .
T h r e e d i f f e r e n t a p p r o a c h e s to t h e s t u d y of t h e s e m a t e r i a l s c a n
be i d e n t i f i e d in the t e c h n i c a l l i t e r a t u r e , e a c h one considering
part of the p h e n o m e n a w h i c h a r e i n f l u e n t i a l o n eutectic morphology.
O n e of t h e s e a p p r o a c h e s , d u e to M a r a t r a y a n d N a n o t ( 1 ) , is based
on the p a r t i t i o n of space d u r i n g s o l i d i f i c a t i o n . From this point
of v i e w the a u s t e n i t e v o l u m e b e i n g s m a l l or l a r g e , c o n d i t i o n s t h e
e x t e n s i o n o f t h e g r o w t h of e u t e c t i c a g g r e g a t e . A n o t h e r approach a t -
t r i b u t e s e u t e c t i c s h a p e c h a n g e s to a l l o y c h e m i s t r y differences ,
particularly explaining M7C3 eutectic refinement as an
e f f e c t of c h r o m i u m content v a r i a t i o n ( 3 ) . F i n a l l y the refinement
of c u t e c t i c s t r u c t u r e is a s s o c i a t e d w i t h f a s t e r c o o l i n g r a t e s ( A ) .

M o l y b d e n u m h a s b e e n e x t e n s i v e l y e m p l o y e d as a l l o y i n g clement in
h i g h c h r o m i u m w h i t e c a s t i r o n s m a i n l y in o r d e r to e n h a n c e h n r d e n a b i I i ty
w i t h o u t s u b s t a n c i a l r i s i n g o f t h e t e m p e r a t u r e o f s t a r t of m a r t e n s ite
f o r m a t i o n t h u s a v o i d i n g l a r g e r a m o u n t s o f r e t a i n e d austenite after
quench. This accounts formany research works which have bucn
carried o u t o n t h eeffect of molybdenum o n heat treating, whereas
o n l y s c a r c e s t u d i e s a r e t o be. f o u n d i n l i t e r a t u r e dealing with
m o l y b d e n u m e f f e c t o n solidification m icro structurc o f F e - C r - C a l l o y s .

J e l l i n g h a u s ( 5 ) , i n o n e o f t h e f e w s t u d i e s ever carried o u t on the

e f f e c t s o f c h r o m i u m a n d m o l y b d e n u m o n t h e solidification s t r u c t u r e ,
found that t h e joint a d d i t i o n o f these t w o elements to Fe-Cr-C
a l l o y s b r o u g h t a b o u t a d e c r e a s e o f t h e l i q u i d u s s u r f a c e temperature.
Also, h e concluded that t h ecarbides could be either M02C or M^C
a c c o r d i n g to t h e p r e v a l e n t % C r / % C relationship a n d to t h e m o l y b d e -
num content of the alloy.

2. Experimental Mate.tiia.l6 and Method*

S t a r t i n g w i t h t w o b a s e a l l o y s containing 15% or 2 0 % c h r o m i u m a n d
2 , 3 % c a r b o n , s e v e r a l r e m e l t i n g o p e r a t i o n s w e r e c o n d u c t e d in o r d e r t o
o b t a i n e i g h t e e n c h e m i c a l c o m p o s i t i o n s c o r r e s p o n d i n g to eu tec tic a n d
hypoeutectic alloys. T h e final analyses showed Cr and Mo contents
v e r y c l o s e to t h e a i m e d o n e s , w h e r e a s a c t u a l c a r b o n contents o b -
tained a r e shown in Table 1.

Cylindrical test pieces were obtained by pouring the molten

alloys into regular shell sand cups for thermal a n a l y s i s , having
30mm internal diameter and about 50mm height, fitted with an
axialy positioned chrome1-alumel thermocouple.

T h e m e t a l w a s p o u r e d d i r e c t l y f r o m t h e s i l i c o n c a r b i d e crucible
into the thermal analysis cups. This practice allowed adequate
p o u r i n g t e m p e r a t u r e c o n t r o l , w h i c h w a s k e p t between 1 4 5 0 a n d 1 4 6 0 ° C
for 1 5 % C r a l l o y s a n d 1 4 8 0a n d 1 5 0 0 ° C f o r 2 0 % C r a l l o y s .

Meta 11ographic samples were taken from transverse slices cut

from t h e c y l i n d r i c a l test pieces at a location immediately above
t h e t h e r m o c o u p l e t i p so a s to a s s u r e c o r r e l a t i o n between microstruc -
ture and thermal analysis.

The v o l u m e t r i c fractions of c o n s t i t u e n t s were d e t e r m i n e d using

a 25 point grid, by making 30 counts per sample, according to
ASTM-E-5G2-76 standard.

Carbide particles were counted with the aid of a 0,31hmm p e -

rimeter circle and expressed as counts per unit length of line.

3. Result* ayid Vi'6cu6i ion

3.1 - l$% _Chh.qmium _atlqiji _co ntaininj)., zg'jo., ^l L$ _ay4_ti § | _ »»0 C f/ br

dctiam.
As a g e n e r a l r u l e , t h e results o b t a i n e d in t h e e x p e r i m e n t s per-
f o r m e d w i t h a l l t h e 1 5 %c h r o m i u m a l l o y s , r e g a r d l e s s o f m o l y b d e n u m
c o n t e n t , w e r e s i m i l a r l y a f f e c t e d by c a r b o n c o n t e n t : as carbon
c o n t e n t w a s i n c r e a s e d , a u s t u n i t e and cu tec tic t e m p e r a t u r e arrests
d e c r e a s e d , w h e r e a s i n c r e a s e d c a r b i d e v o l u m e f r a c t i o n s and carbitie
p a r t i c l e s n u m b e r s w e r e d e t e c t e d in b o t h e u t e c t i c a n d t o t a l vol-
umes .

Thermal a n a l y s i s - Table 1 presents the a u s t e n i t e and cutectic

t e m p e r a t u r e a r r e s t s as a f f e c t e d by c a r b o n c o n t e n t , f o r z e r o , 1,5
and 2 , 5 % m o l y b d e n u m a l l o y s . T h e s e s a m e r e s u l t s a r e a l s o s h o w n in
f i g u r e 1. A u s t e n i t e t e m p e r a t u r e a r r e s t e x h i b i t s a m a r k e d decrease
a s t h e e u t c c t i c c o m p o s i t i o n is a p p r o a c h e d . T h e p r o x i m i t y of
e u t e c t i c c o m p o s i t i o n may be a p p r a i s e d f r o m f i g u r e 2 .

These results show that higher carbon contents provoke also a

d e c r e a s e of the e u t c c t i c r e a c t i o n t e m p e r a t u r e . T h e fact that
d i f f e r e n t s o l i d i f i c a t i o n p a t h s a r e f o l l o w e d i n e a c h c a s e as s h o w n
in f i g u r e 2 , a f f o r d s an e x p l a n a t i o n for t h i s e f f e c t - In f a c t , as
figure 2 shows s c h e m a t i c a l l y , the h i g h e r the c a r b o n c o n t e n t , the
l o w e r t h e t e m p e r a t u r e a t w h i c h t h e e u t e c t i c m o n o v a r i a n t l i n e U^-ej_
is r e a c h e d .

A s c o m p a r e d to z e r o m o l y b d e n u m c o n d i t i o n , a d d i t i o n s of 1,5 o r
2 , 5 % M o l e a d to s m a l l b u t s i g n i f i c a n t d e c r e a s e in a u s t e n i t e t e m -
p e r a t u r e a r r e s t for the 2 , 3 % C a l l o y . No e f f e c t of t h i s kind is
o b s e r v e d for 3% C a l l o y p r o b a b l y as a r e s u l t of the s t r o n g i n f l u
ence w h i c h s m a l l v a r i a t i o n s of b o t h the c a r b o n c o n t e n t and the
c o o l i n g r a t e e x e r t o n a u s t e n i t e t e m p e r a t u r e a r r e s t (T a ) .

S i m i l a r d i f f i c u l t i e s w e r e m e t w i t h 2 0 % c h r o m i u m alloys, although
d e c r e a s e s in a u s t e n i t e t e m p e r a t u r e a r r e s t s w i t h m o l y b d e n u m a d d i -
t i o n s a r e r e p o r t e d b y K i r k a l d i ( 6 ) f o r s t e e l s a n d by J e l l i n g h a u s (5)
for F e - C r - C - M o a l l o y s .

It m a y be c l e a r l y n o t i c e d in f i g u r e 1 a p r o g r e s s i v e reduction
of e u t e c t i c t e m p e r a t u r e a r r e s t as m o l y b d e n u m a d d i t i o n s are made
at s a m e c a r b o n l e v e l . Q u i t e s i m i l a r r e s u l t s w e r e o b t a i n e d by
M a t s u b a r a ( 7 ) : b y a d d i n g M o to 15 a n d 3 0 % c h r o m i u m a l l o y s , lie
d e t e c t e d l o w e r t e m p e r a t u r e s of s t a r t a n d end of eutectic solidi-
fication.

It c a n t h u s b e s t a t e d t h a t m o l y b d e n u m a d d i t i o n s u p to 2,5%
a l t e r s t h e s o l i d i f i c a t i o n p a t h o f t h e a u s t e n i t e , c h a n g i n g the F e - C r - C
t e r n a r y p h a s e d i a g r a m , t h o u g h not s e v e r e l l y r e s t r a i n i n g its use
as a t e c h n o l o g i c a l t o o l for the i n t e r p r e t a t i o n of s o l i d i f i c a t i o n
p r o c e s s in c o m m e r c i a l a l l o y s .

v
Quantitative metallography: Austen itc volume fraction ( a)
and Car b i d e ' v o l u m e f r a c t i o n ("V v k ) .

T a b l e 2 and f i g u r e 3 show t h a t , for m o l y b d e n u m free alloys

(solid l i n e s in f i g u r e 3) , Vv a d i m i n i s h e s as the c a r b o n content
is i n c r e a s e d .
T h i s f a c t t o o is e x p l a i n e d by the c l o s e r p r o x i m i t y of h i g h e r
 v
c a r b o n a l l o y s to the e u t e c t i c l i n e . T h e o b s e r v e d d e c r e a s e of n
i s m u c h m o r e m a r k e d f o r t h e 3 , 0 t o 3 , 6 % C c h a n g e tltnn f o r t h e 2,3
to 3 ,0%C c h a n g e /

F i g u r e 3 s h o w s a l s o t h a t t h e a d d i t i o n o f m o l y b d e n u m e n t a i l e d an
i n c r e a s e in a u s t e n i t e v o l u m e f r a c t i o n , but no s i g n i f i c a n t c h nn ye
o f ^ v a c a n b e d e t e c t e d w h e n m o l y b d e n u m a d d i t i o n i s r a i s e d from 1 , 5
t o 2 , 5 %. T h e s e o b s e r v a t i o n s s u g g e s t t h e o c c u r r e n c e o f c h a n g e s in
the s o l i d i f i c a t i o n p a t h s w h e n m o l y b d e n u m is a d d e d , so that the
e u t e c t i c l i n e w o u l d b e r e a c h e d o n l y w h e n a l e s s e r q u a n t i t y of liquid
would remain for the e u t e c t i c s o l i d i f i c a t i o n . A p p a r e n t l y , t h o u g h ,
some mechanism l i m i t s t h i s a u s t c n i t e p r o m o t i n g e f f e c t of molyb-
denum.

As s t a t e d in the l i t e r a t u r e ( 1 , 8 ) , the c a r b i d e v o l u m e f r a c t i o n
v k i n c r e a s e s a s c a r b o n c o n t e n t i s i n c r e a s e d , but m o l y b d e n u m a p p a r e n t l y
d o e s n o t i n f l u e n c e ^ v k ; t h e s a m e c o n c l u s i o n c a n be d r a w n by com-
p u t i n g d a t a f r o m M a r a t r a y (1) and Z u m - G a h r ( 8 ) .

Q u a n t i t a t i v e m e t a l l o g r a p h y : Carbide particle number per line

l e n g t h in t h e t o t a l v o l u m e a n d in t h e e u t e c t i c v o l u m e .

A s s h o w n in T a b l e 3 a n d f i g u r e A , t h e c a r b i d e p a r t i c l e count in
t o t a l v o l u m e ( N t £ ) i n c r e a s e s w i t h c a r b o n c o n t e n t up to eutectic
c o m p o s i t i o n , b o t h in a l l o y s w i t h and w i t h o u t m o l y b d e n u m . This
f e a t u r e w a s p r e d i c t a b l e s i n c e it is a d i r e c t c o n s e q u e n c e o f t h e d e -
c r e a s e of v v a as the c o m p o s i t i o n c o m e s n e a r e r the e u t e c t i c l i n e .

In o r d e r to a s c e r t a i n t h e e f f e c t s o f c a r b o n a n d m o l y b d e n u m on
the s o l i d i f i c a t i o n s t r u c t u r e s of the e u t e c t i c microconstituents
i n d e p e n d e n t l y of the a u s t e n i t e v o l u m e f r a c t i o n , the n u m b e r or car
b i d e p a r t i c l e s per u n i t l e n g t h of l i n e in the e u t e c t i c r e g i o n w a s
c o m p u t e d as
N
e£ = Nt£/(1-Vva)

i.e, those p a r t s of the line c r o s s i n g the austenite region are

subtracted from the total line length.

When p l o t t e d a g a i n s t % C a r b o n , f i g u r e A , ^ e£ c a l c u l a t e d v a l u e s
e x h i b i t a v e r y p r o n o u n c e d d e c r e a s e w h i c h , t o g e t h e r w i t h the con-
c u r r e n t d e c r e a s e o f ^ v a , r e f l e c t a c o a r s e n i n g o f t h e e u t e c t i c cajr
b i d e s . A n a n a l o g o u s b e h a v i o u r is e n c o u n t e r e d a m o n g g r e y cast i r o n s
w h e r e the v e r y b r a n c h e d u n d e r c o o l e d g r a p h i t e m o r p h o l o g i e s (types
D and E ) g i v e w a y to the c o a r s e r A t y p e w h e n c a r b o n equivalent
a p p r o a c h e s the e u t e c t i c v a l u e , o t h e r f a c t o r s as b a t h c o n d i t i o n an
cooling rate kept unchanged.

T w o f a c t o r s m a y b e c o n s i d e r e d to i n f l u e n c e t h e r e f i n i n g of
e u t e c t i c c a r b i d e s . T h e f i r s t o n e r e l a t e s to t h e p a r t i t i o n of
space among the a u s t e n i t e d e n d r i t e s and the e u t e c t i c : the more
h y p o e u t e c t i c the a l l o y , the less w i l l be the v o l u m e of liquid
r e m a i n i n g f o r e u t e c t i c s o 1 i d i f i c a t i o n ,. g i v i n g s m a l l e r eutectic
c e l l s . T h e s e c o n d f a c t o r i s a c h e m i c a l o n e : the m o r e h y p o e u tec tica
 t h e a l l o y , tlic h i g h e r w i l l b e b o t h t li G e u t e c t i c a r r e s t and the
c h r o m i u m c o n t e n t of the l i q u i d at the e u t e c t i c f r e e z i n g , as may
be s e e n in f i g u r e 2. T h i s c o u l d c a u s e c a r b i d e r e f i n i n g s i n c e ,
a c c o r d i n g to M a t s u b a r a ( 7 ) , the h i g h e r the c h r o m i u m c o n t e n t of
e u t e c t i c a l l o y s , the finer will be the c a r b i d e s and the shorter
w i l l be the s o l i d i f i c a t i o n r a n g e .

A microstructural analysis reveals:

1) lengthier carbides as carbon content is raised from 2,3 to 3,0%

2) t h i c k e r c a r b i d e s at i n c r e a s i n g d i s t a n c e s from e u t e c t i c cells'
c e n t e r s ; t h i s c o a r s e n i n g is m o r e m a r k e d f o r t h e 3 , 0 % C alloy
than for the 2,3% C o n e .

3) m o r e h e x a g o n a l and c o a r s e c a r b i d e s at e u t e c t i c cell edge for

the h i g h e r carbon c o n t e n t s ; these c a r b i d e s are t h e b u l k i e s t in
the eutectic alloy.

The foregoing remarks are schematically represented in figure 5 .

T h e i n c r e a s i n g i n t e r - c a r b i d e s p a c i n g s as t h e e u t e c t i c cell bound-
a r y is a p p r o a c h e d c a n b e e x p l a i n e d m a k i n g r e f e r e n c e t o t h e s o l i d i f i
c a t i o n s e q u e n c e of a e u t e c t i c a l l o y . S o l i d i f i c a t i o n s t a r t s witli
n u c l e a t i o n of e u t e c t i c c o l o n i e s ; as the e u t e c t i c c e l l s become
l a r g e r , the t e m p e r a t u r e and the c o m p o s i t i o n follow the eutectic
l i n e f r o m U ] t o e-^ , f i g u r e 2 . I n o t h e r w o r d s t h e e u t e c t i c s o l i d i -
f i c a t i o n w o u l d t a k e p l a c e a t d e c r e a s i n g t e m p e r a t u r e s if equili-
b r i u m w e r e to b e a t t a i n e d . H o w e v e r , t h e s o l i d i f i c a t i o n actually
t a k e s p l a c e , at l e a s t p a r t i a l l y , at a c o n s t a n t t e m p e r a t u r e (the
e u t e c t i c a r r e s t ) . T h e r e f o r e the a c t u a l s o l i d i f i c a t i o n p r o c e s s o c -
c u r s at g r a d u a l l y s m a l l e r u n d e r c o o l i n g s a s e u t e c t i c solidification
p r o c e e d s , a s r e p r e s e n t e d i n f i g u r e 6. S m a l l e r u n d e r c o o l i n g s r e d u c e
the c a r b i d e b r a n c h i n g f r e q u e n c e and, consequently inter-par-
.ticle s p a c i n g s are increased as the e u t e c t i c c e l l b o u n d a r y a d -
v a n c e s . A n o t h e r p o s s i b l e e x p l a n a t i o n f o r t h e o b s e r v e d i n c r e a s e in
c a r b i d e p a r t i c l e s p a c i n g s m i g h t b e tlie s o l u t e g a t h e r i n g a t l i q u i d
e u t e c t i c c e l l i n t e r f a c e , t h u s c h a n g i n g c o n s t i t u t i o n a l undercooling.
The c a r b i d e t h i c k e n i n g and the p r e s e n c e of h e x a g o n a l carbides
at cell b o u n d a r i e s a d m i t a s i m i l a r e x p l a n a t i o n . At the s t a r t of
e u t e c t i c f r e e z i n g , when higher u n d e r c o o l i n g s p r e v a i l , the driving
f o r c e i s l a r g e a: i < • u g h t o s u p p o r t t h e h i g h b r a n c h i n g f r e q u e n c y a n d
the c r e a t i o n of interfaces b e t w e e n a u s t e n i t e and car-
b i d e at the e u t e c t i c c e l l . B o t h c a r b i d e and a u s t e n i t e a d o p t then
the m o r p h o l o g y w h i c h is a d e q u a t e for f a s t g r o w t h . A f t e r w a r d s , at
l o w e r u n d e r c o o l i n g s , t h e d r i v i n g f o r c e is l e s s i n t e n s e , causing
t h e c a r b i d e s to c h a n g e tlieir s h a p e i n o r d e r to s p e n d l e s s s u r f a c e
e n e r g y . A n e v i d e n c e w h i c h c o r r o b o r a t e s tliiy e x p l a n a t i o n is the
p r e s e n c e at c e l l b o u n d a r i e s of c a r b i d e s h a v i n g h e x a g o n a l cross-sec-
t i o n , w h i c h is t h e e q u i l i b r i u m f o r m of C r 7 C 3 -

Additions of m o l y b d e n u m c a u s a the c a r b i d e p a r t i c l e c o u n t s both

in the t o t a l v o l u m e a n d in t h e e u t e c t i c v o l u m e to d e c r e a s e , and
the carbides to c o a r s e n , c o n f i r m i n g t h e o b s e r v a t i o n s m a d e by
M a t s u b a r a Tor c u t c c t i c a l l o y s , ( 7 ) . This could be attributed to mo-
l y b d e n u m s e g r e g a t i o n out. of the c u t o c t i c c o l l .

N o c l e a r d i f f e r e n c e b e t w e e n c a r b i d e p a r t i c l e c o u n t s is noted f o r
the two d i f f e r e n t m o l y b d e n u m a d d i t i o n s (1,5 and 2 , 5 % M o ) , s u g g e s t i n g
t h e e x i s t e n c e of s o m e s o r t of l i m i t for t h i s e f f e c t of m o l y b d e n u m ,
m u c h i n t h e s a m e l i n e o f w h a t w a s s a i d a b o v e in r e l a t i o n to the
austenite volume fraction. This limiting mechanism will recur in
2 0 % c h r o m i u m a l l o y s , so t h a t , w i t h i n t h e l i m i t s o f t h e s e experi-
ments, V v a , e£ and c
£ a r e s e n s i t i v e to m o l y b d e n u m p r e s e n c e but
a p p a r e n t l y i n s e n s i t i v e to i t s a c t u a l c o n t e n t .

T h e w i d e n i n g of i n t e r - c a r b i d e s p a c i n g s as a r e s u l t of molybde-
n u m a d d i t i o n h a s b e e n a t t r i b u t e d by M a t s u b a r a a n d c o - w o r k e r s ( 7 ) t o
a n e n l a r g e m e n t o f t h e e u t e c t i c f r e e z i n g r a n g e c a u s e d bu this e l e m e n t .
T h i s e f f e c t i s p r o b a b l y r e l a t e d to t h e s e g r e g a t i o n o f m o l y b d e n u m to
the liquid d u r i n g f r e e z i n g .

T h e m a n n e r in w h i c h c a r b o n a n d m o l y b d e n u m a f f e c t t h e variables
m e a s u r e d is the s a m e f o r 2 0 % c h r o m i u m - as f o r 1 5 % c h r o m i u m a l l o y s .
A s c a r b o n c o n t e n t is i n c r e a s e d , a u s t e n i t e and eutecli. c a r r e s t s b e -
c o m e p r o g r e s s i v e l y l o w e r , ^ v a and N e £ d e c r e a s e , w h i l e " v k increases.
T h e e f f e c t s o f a d d i n g m o l y b d e n u m to 2 0 % c h r o m i u m a l l o y s a r e also
v e r y s i m i l a r to t h o s e o b s e r v e d f o r 1 5 % c h r o m i u m a l l o y s .

When the c h a r a c t e r i s t i c s of 2 0 % c h r o m i u m . a l l o y s a r e compared

to t h o s e o b t a i n e d i n 1 5 % c h r o m i u m a l l o y s , t h e f o l l o w i n g g e n e r a l o_b
servations are evident:

a) 15% chromium alloys present lower austenite and eutectic arrests;

b) at a n y g i v e n c a r b o n c o n t e n t , V v a is s m a l l e r f o r 2 0 % chromium
alloys b e c a u s e these are n e a r e r the e u t e c t i c m o n o v a r i a n t l i n e .
e
c ) "*-<£ a n d t a r e l a r g e r f o r 2 0 % c h r o m i u m a l l o y s as c o n s e q u e n c e s
o f t h e s m a l l e r a u s t e n i t e v o l u m e f r a c t i o n and of t h e s h o r t e r
eutectic freezing range.
 REFERENCES
(1) M A R A T R A Y , F. & U S S E C L I O - N A N O T , R. - " F a c t o r s a f f e c t i n g the
s t r u c t u r e of c h r o m i u m and c h r o m i u m - m o l y b d e n u m w h i t e i r o n s " .
C l i m a x M o l y b d e n u m C o . , 1 9 7 0 , 32 p.

(2) P O W E L L , G . L . F . - " M o r p h o l o g y of e u t e c t i c M 3 C and M 7 C 3 in white

irons c a s t i n g s " . M e t a l s F o r u m , 2» ( l ) : 3 7 - 4 2 , 1 9 8 0 .

(3) M A T S U B A R A , Y . ; O G I , K. & M A T S U D A , K. - " E u t e c t i c s o l i d i f i c a - .

tion of h i g h - c h r o m i u m cast i r o n - e u t e c t i c s t r u c t u r e s and their
q u a n t i t a t i v e a n a l y s i s " . T r a n s a c t i o n s A F S , ]_!_'. 1 8 3-1 9 6 , 1981

(4) G O O S S E N S , L . J . M . ; C A R P I N E T T I O O S T A , P.H.; SOUZA S A N T O S , A.'B .-

" O b s e r v a g o e s r e l a t i v a s as i n f l u e n c i a s do teor de c a r b o n o em
f e r r o s f u n d i d o s b r a n c o s com 1 5 % Cr e 3% M o " . M e t a l u r g i a - A B M ,
3_5(262) : 5 9 1 - 6 , 1 9 7 9 .

(5) JELL1NGI1AUS , W. - "Zur K e n n t n i s des V i cr s to f f - Systems Eisenchrom-

M o 1 y b d a n - K o h i e n s t o f f " . A r c h i v fur das E i s e n h u t t e n w e s e n . 4 2 .
(2) : 1 3 3 - 1 4 2 , .1971 .

(6) K I R K A L D Y J . S . ; T H O M S O N , B . A . & B A G A N 1 S , E . A . - " P r e d i c i t i o n o f

m u l t i c o m p o n e n t e q u i l i b r i u m and t r a n s f o r m a t i o n for low alloy
s t e e l s " . H a r d en a b i 1 i t y c o n c e p t s w i t h a p p l i c a t i o n s to steel (I'roc).
Chicago (USA) 24-26 out 1 9 7 7 . M e t . Society A I M E . 1 9 7 8 .

(7) M A T S U B A R A , Y ; O G I , K . & M A T S U D A , K . - " I n f l u e n c e of alloying

e l e m e n t s o n t h e eutectic s t r u c t u r e s of h i g h c h r o m i u m cast irons".
I m o n o , 5J^ ( 9 ) : 5 4 5 - 5 5 0 , 1 9 7 9

(8) Z U M GA11R, K . H . ; & E L D I S , G . T . - " A b r a s i o n wear of w h i t e cast

i r o n s " . W e a r , 6 4 :1 7 5 - 1 9 4 , 1 9 8 0 .
T (°C) 1350 15%Cr
— O%Mo
— 1,5% Mo
•— 2 , 5 % Mo

1300

1250

1200
2,2 2,6 3,0 3,4 3,0
%C

I•*If». I A t i s l n i i l o I n n p p r a h i i v :uul
f i l l I ' l l | C I MHpnnil III '•' i

Pig. 2 Liquidus surface of Fo-Cr-C plinsc dinprniu

Shcmnlic s o l i d i f;ic;ition paths for a l l o y s
with 15"u Cr - 2 , 3 ( 1 ) ; 2,9(2) and 3,6°.C
%V v y 00 r 10% Cr
0 % Mo
_ 1,5% Mo
.— 2 , 5 % Mo

Fig. 3 - Volume fraction of primary austenite V :,

Va
as a function of carbon content.
200 15%Cr
0 % Mo
1 , 5 % Mo
*~ • ——— • 2 , 5 °/o M o

LE

150

100

50

2,2 2,6 3,0 3,4 3,8

%C
Fig. 4 - Eutectic particle number in total volume
(N 1) and in cutcctic volume (N .) as a
fuuCion of carbon content.
Fig. 5 Morphology of eutectic cell form increasing
carbon contents (1) 2,3°&; (2) 2,9?« and (3) 3,6°»C

t (min)

Fig.C) Underc-ooling clK during cutcctic

solidification
 Tt'Cl

Mill) -

12VI

I 2nd LLi,
2,1 .'.'• '•.«> '.'

Fig. 7 Effect of Cr, C, and Mo on nustenite and

eutectic temperature
1
• arrest (Ta and Te)

Vvr(l,5 MO)

20 -

Fig. 8 Effect of Cr, C and Mo on austcntte

volume fraction (V,,,,)
V<1
 Hue)
200
N. , |O M0|

(1*3)

150
(Ml)

1U0

%c

Fig. 9 Effect of Cr, C and Mo on carbide particle

number in total volume (N ,) ajid in euiectic
L
volume (N cl )
TABLE 1 - Carbon contents, austcnitc and eutcctic
t o in p c r n L u r c n r r c s t is .

1
• i •••""••—-™ ' '

Allo y « I C
TY('C)
(Cr-C-Mo)
15 - 2,3 - 0 2,25 13 21 1253
15 - 3,0 - 0 2,94, 1281 1238
15 - 3,6 - 0 3, 5 2 - 1229
IS - 2,3 - 1,5 2,21 124 6 1317
15 - 2,3 - 2,5 2,24 1240 1308
IS - 3,0 - 1,5 2,94 1232 1281
15 - 3,0 - 2,5 2,99 .12 27 1281
15 - 3,6 - 1,5 3,4 3 1224 1224
15 - 3,6 - 2,5 3,65 1217 1217
20 - 2,3 - 0 2,24 1331 1263
20 - 3,0 - 0 2,95 128 5 1254
20 - 3,6 - 0 3,44 - 1244
20 - 2,3 - 1.5 2,20 12 50 ND
20 - 2,3 - 2,5 2, 20 1243 13 21
20 - 3,0 - 1,5 3,01 1242 1266
20 - 3,0 - 2,5. 3,09 1238 1263
20 - 3,6 - 1,5 3,44 123 5 1235
20 - 3,6 - 2,5 3,55 1230. 1230
TABLE 2 - Volume fraction of austcnite and
volume fraction of carbide

A11 o y s vv o r\
>/
( C r - C - M o ;)

15 - 2,3 - 0 58,7 + 3,1 16,1 _+ 2,7

15 - 3,0 - 0 41,7 + 3,3 2 5 , 2 jf 3,4
15 - 3,6 - 0 0 28,6 + 3,5
15 - 2,3 - 1,5 65,6 + 3,2 17 ,0 +_ 2,5
15 - 2,3 - .2,5 6 4,1 4,1 14,8 +_ 1,6
15 - 3,0 - 1,5 54 ,4 + 3,5 25,4 + 2,5
15 - 3,0 - 2,5 53,1 +. 2,8 2 3,6 + 2,5
15 - 3,6 - 1,5 0 25,5 + 2,9
15 - 3,6 - 2,5 0 31,3 + 3,3
20 - 2,3 - 0 5 6,0 + 2,6 15,6 ^ 2,7
20 - 3,0 - 0 3 3,1 + 3,2 24,7 + 2,8
20 - 3,6 - 0 0 32,3 + 3,5
20 - 2,3 - 1,.5 61,9 + 4,2 19,9 + 2,0
20 - 2,3 - 2,5 59,1 3,5 18,4 + 3,2
20 - 3,0 - 1,5 3 5,4 3,4 26,0 + 2,3
20 - 3,0 - 2,5 38,0 + 3,5 25,3 + 3,1
20 - 3,6 - 1,5 0 32,5 + 3,0
20 - 3,6 - 2,5 0 31,1 +_ 3,4
TAULIi 3 - K u L o c t i c c a r b i d e p;i r L i e I o n u m b e r in
total, v o l u m e (N t £ ) and in eutectic
volume (Ne£) .

Allbys N I.,.
(Cr - C - Mo) \,

15 - 2,3 - 0 75, 1 - 7,5 181 ,'7 - 11,1

15 - 3,0 - 0 82, 2 - 6,.9 14 1 .3 - 9.4
15 - 3,6 - 0 84, 6 - 6,5 81 ,6 - 6.5
15 - 2,3 - 1,5 48, 8 - 4.6 141 ,7 - 9,6
15 - 2,3 - 2, 5 50, 6 - 7.2 140 .9 - 9,4
15 - 3,0 - 1. 5 59, 6 - 5,5 130 ,8 - 8,9
15 - 3,0 - 2, 5 64, 3 - 5,3 137 ,7 - 8.3
15 - 3,6 - 1,5 67, 4 - 4,7 6 7 .4 - 4.7
15 "X f\
O , \)
2, 5 80, 1 - 7,9 80 ,1 - 7.9
20 - 2,3 - 0 90, 0 - 8,9 195 ,7 - 12,3
20 - 3,0 - 0 97, 8 - 7,1 146 ,1 - 9,4
20 - 3,6 - 0 92, 5 - 6,8 92 ,5 - 6,8
20 - 2,3 - 1, 5 63, 8 - 6,9. 165 ,0 - 9,5
20 - 2,3 - 2, 5 64, 5 - 5, 5 157 .0 - 9,7
20 - 3,0 - 1, 5 77, 8 - 5,3 131 ,4 - 6,6
20 - 3,0 - 2, 5 71, 6 - 6,0 11 5 .5 - 8,3
20" - 3,6 - 1, 5 74, 5 - 5,5 7 4 ,5 - 5,5
20 - 3 , 6 - 2, 5 79, 5 - 5,6 7 9 ,5 - 5,6