DAVID N . FRENCH, INC.
, METALLURGISTS
FALL 1988
NORTHBOROUGH. MASSACHUSETTS 01532
A VIEW FROM THE PENTHOUSE: USEFUL INFORMATION FOR THE WORLD OF BOILERS
EQUILIBRIUM MICROSTRUCTURES
Plain-carbon and low-alloy s t e e l s a r e the
most camon and useful engineering materials.
They a r e strong, weldable, corrosion and
oxidation-resistant, have good high-tempera-
t u r e properties, and a r e inarpensive.
Unalloyed iron ( o r f e r r i t e ) is, by comparison,
too weak t o be useful. Additions of alloying
elements (usually manganese, silicon.
chromium, and molybdenum) increase the f e r r i t e
strength. Small additions (<0.3%)of carbon
further imprwe the strength of these alloys
by the formation of metastable microstructures
based on iron carbide. During elevated-
temperature b o i l e r service these metastable
structures change w e r time t o equilibrium
structures, some q u i t e unusual and uncommon.
F e r r i t e is an i n t e r s t i t i a l s o l i d solution
of carbon and the low-temperature form of
iron. Carbon is a small atom and f i t s i n t o
the "holes" between iron atoms, hence the term
" i n t e r s t i t i a l . " Alloying elements s u b s t i t u t e
for iron atoms within f e r r i t e also. Iron
carbide has a specific composition, Fe3C, but
iron may be replaced by other elements,
especially chromium, which is a potent carbide
former on i t s own. Both chromium and
molybdenum with iron form a complex carbide,
M23C6, where lW1 is the metal atom.
From a thermodynamic o r i n t e r n a l energy
viewpoint, f o r plain carbon s t e e l s , the s t a b l e
o r equilibrium structure is f e r r i t e and
graphite. The addition of about 1/2% chromium
s t a b i l i z e s the Fe3C so that decomposition i n t o
f e r r i t e and graphlte does not occur.
There a r e other metastable structures t h a t
form during rapid cooling of these alloys from
metalworking temperatures of 1700'-1800°F t o
room temperature. A t these e l w a t e d tempera-
tures, the structure is a l l austenite, a s o l i d
solution of carbon i n the high-temperature
form of iron, which transforms on cooling t o
f e r r i t e and iron carbide a t temperatures below
1340°F. The r a t e of cooling determines the
final microstructure: a quench w i l l form
martensite o r bainite, depending on the
cooling rate. Since these metastable
O N E LANCASTER ROAD VOL. Vn NO. 3
(508) 393-3635
structures a r e not found i n b o i l e r components
(except perhaps i n heat-affected zones of
welds o r i n high-temperature f a i l u r e s ) , no
further discussion is necessary.
The usual heat treatment is t o cool
slowly t o room temperature. This is known as
a llnormalizing heat treatment" and the f i n a l
structure would be "normalized. " The
llnormalll structure, following such a
treatment, is f e r r i t e and p e a r l i t e , see
Figure 1. This structure of f e r r i t e and
p e a r l i t e is c h a r a c t e r i s t i c of plain-carbon
Figure 1
s t e e l s , SA-178. SA-210, o r SA-106. f o r
example.
The amount of p e a r l i t e depends on the %
carbon: the higher the carbon content, the
larger the amount of p e a r l i t e . P e a r l i t e is
made up of a l t e r n a t e layers of f e r r i t e and
iron carbide. The Fe3C shape i n p e a r l i t e is
a blade o r plate, large i n two dimensions and
small i n the third. Such a shape has a large
surface t o volume r a t i o . By changing shape
t o spherical p a r t i c l e s , this S/V r a t i o is
reduced, and the internal energy tends toward
a minimum.
The f u l l y annealed condition f o r a plain-
carbon s t e e l would have the iron carbide i n a
spheroidized form. This same structure
occurs i n b o i l e r s t e e l s a f t e r prolonged
operation. The i n t e r n a l energy of Fe3C is
reduced by the change from a p l a t e shape t o a
spherical one, see Figure 2. The
microstructure is s t i l l f e r r i t e and iron
carbide, but the large surface t o volume
r a t i o has been reduced.

Figure 2
These structures a r e still considered
metastable f o r plain-carbon s t e e l s i n t h a t t h e
lowest-internal-energy form has s t i l l not yet
been reached.
The t r u e equilibrium microstructure of
plain-carbon and carbon +1/2 molybdenum
s t e e l s is the formation of f e r r i t e and
graphite. The transformation of iron carbide
t o f e r r i t e and graphite further reduces the
internal energy, see Figure 3.
Figure 3
Graphite does not form i n low-carbon steels
during cooling from 1800°F because the
nucleation of iron carbide is more e a s i l y
accomplished than t h e nucleation of graphite.
Thus the formation of f e r r i t e and metastable
iron carbide occurs r a t h e r than the s t a b l e
graphite because the nucleation k i n e t i c s favor
Fe3C formation.
The decomposition of iron carbide i n t o
ferrite and graphite occurs i n plain-carbon
and carbon-molybdenum steels similar t o SA-
209. 1/Z chromium prevents the decomposi-
t i o n of the carbide i n t o f e r r i t e and graphite.
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Thus f o r the chromimmnolybdenum s t e e l s
similar t o T-11 and T-22 t h e equilibrium
microstructure is one of f e r r i t e and
spheroidized carbides, similar t o Figure 2.
One further but unusual change i n
microstructure occurs a t low-operating tew
peratures, a f t e r a very long time. F e r r i t e
is a s o l i d solution of iron and carbon. A t
1350°F, 0.02% carbon w i l l dissolve i n
f e r r i t e . A t room temperature, the s o l i d
s o l u b i l i t y i n f e r r i t e is estimated t o be
<0.0005% C. Thus f e r r i t e is usually
supersaturated r e l a t i v e t o carbon. This
presents no unusual microstructural features
when t h e operating temperatures a r e i n the
700°0r 800°F temperature range. Carbon atoms
a r e s u f f i c i e n t l y mobile t h a t equilibrium
between the carbon dissolved i n f e r r i t e and
iron carbide is r e l a t i v e l y quickly achieved.
For steam piping t h a t has been i n operation
f o r many years a t a temperature of 300°F, the
circumstance is s l i g h t l y different.
Figure 4
Figure 4 shows the equilibrium structure
from a plain-carbon s t e e l pipe i n service
since about 1915. The steam temperature w a s
about 300°F. The structure here is f e r r i t e ,
with t i n y graphite p a r t i c l e s within each
f e r r i t e c r y s t a l , and grain-boundary carbides.
The graphite forms along particular crystal-
lographic planes and so appears as rows o r
l i n e s within each f e r r i t e grain. I f the
temperature is higher, the carbon mobility is
great enough t o form large blocks of
graphite, as shown i n Figure 3. It is only
a f t e r very-long service a t temperatures of
20O0-300°F t h a t the structure of Figure 4 is
developed.