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DAVID N . FRENCH, INC.

, METALLURGISTS
ONE LANCASTER ROAD
N O R T H B O R O U G H . M A S S A C H U S E T T S 01532 VUL. VII. ND. 1

A VIEW FROM THE PENTHOUSE: USEFUL INFORMATION FOR THE WORLD OF BOILERS

there a r e s i m i l a r i t i e s t o the microstructure


in that they a l l contain grain-boundary
The morphology of the corrosion damage that corrosion o r cracks.
occurs on t h e water. o r steam s i d e of a b o i l e r Figure 1 shows a c h a r a c t e r i s t i c
tube depends upon several f a c t o r s , among them: microstructure of hydrogen damage. mdrogen
t h e l o c a l metal temperature, microstructure damage occurs i n waterwall tubes under thick.
and s t a t e of stress, deposit thickness, t h e waterside corrosion deposits. One of t h e
oxygen content of t h e b o i l e r water, and t h e pH products of corrosion i s atomic hydrogen
l o c a l l y between t h e deposit and t h e tube which, being a small atom, d i f f u s e s i n t o t h e
metal. This l a t t e r f a c t o r can be steel. mdrogen r e a c t s with i r o n carbide t o
s u b s t a n t i a l l y d i f f e r e n t from the bulk pH. form f e r r i t e and methane. The methane
Deposits a r e porous, and b o i l e r water t u r n s t o molecule i s l a r g e and cannot d i f f u s e through
steam within the deposit. The hydroxide that t h e steel; s o c o l l e c t s a t t h e f e r r i t e grain
was in the water, that is now a steam bubble. boundaries. When t h e methane pressure i s
is l e f t behind within t h e deposit. Gradually s u f f i c i e n t l y g r e a t , intergranular cracks form
the hydroxide concentration increases s o that along t h e f e r r i t e grain boundaries.
l o c a l l y t h e pH can be strongly basic, pH 12 o r
13 even.
Waterside deposits impede t h e heat
t r a n s f e r between t h e tube and t h e steam/water
emulsion. The thermal conductivity of these
deposits is much less than that of t h e s t e e l ;
so there is much l e s s e f f e c t i v e cooling of t h e
tube by t h e f l u i d . The n e t e f f e c t is t o r a i s e
tube-metal temperatures. A s t h e tube-metal
temperature increases, s o does t h e corrosion
r a t e ( g r e a t e r wastage o r wall thinning) and s o
does t h e degradation within t h e
microstructure. These a r e competing Figure 1. 200x
mechanisms in the sense that f a i l u r e s can
occur by both creep and corrosion wastage o r There are two c h a r a c t e r i s t i c f e a t u r e s t o
hydrogen attack. hydrogen damage. 1) intergranular cracks, and
G r a i n boundaries are zones of weakness 2) l o s s of iron carbides (decarburization).
where, on a short-range atomic s c a l e , t h e Figure 1 shows both of these c h a r a c t e r i s t i c s .
atoms a r e not as n e a t l y arranged a s they a r e The cracks a r e q u i t e long, extending wer many
within a c r y s t a l l a t t i c e of an individual grains and some are oxide c w e r e d with
grain. This short-range disorder leads t o a corrosion products.
s l i g h t l y higher i n t e r n a l energy, and corrosion
occurs more rapidly along these grain
boundaries. Atoms a r e more e a s i l y dissolved
from regions of high energy, l e s s energy is
required f o r solution. A t elevated
temperatures, deformation occurs more r e a d i l y
along t h e grain boundaries. Thus creep damage
appears i n t h e microstructure a s voids and
separation along grain boundaries.
What follows is a catalogue of several
microstructural f e a t u r e s that r e s u l t from
water- o r steamside corrosion. I n each case Figure 2. 200x
Figure 2, from the same boiler, shows the
second e f f e c t of thick waterside deposits,
t h a t is, elevated temperatures and creep
damage. The microstructure shows
intergranular creep damage, pr creep voids,
not hydrogen damage. Here the voids appear t o
be no longer than a single c r y s t a l boundary
and a r e more hole than extended crack. The
microstructure along the I D surface of the
tube a t t h i s location shows no intergranular
crackirig t o the f e r r i t e grains. For waterwall
tubes, creep f a i l u r e s usually s t a r t a t the OD
surface a s the metal temperature is 75°-1000F
hotter than a t the I D . Thus, this particular Figure 4. lOGx
f a i l u r e is an elevated-temperature s t r e s s
rupture caused by the waterside deposits. Figure 4 shows grain-boundary corrosion of
That these two microstructures came from a 304 s t a i n l e s s superheater tube. A t
the same b o i l e r indicates the v a r i a b i l i t y of temperatures abwe about 1050°F, chromium
waterside corrosion, depending on the local carbides form along the austenite grain
heat flux (metal temperature), pH (which boundaries. The formation of these carbides
governs the corrosion r a t e ) , and deposit depletes the austenite grains of chromium
thickness as it a f f e c t s tube-metal adjacent t o the grain boundaries. As the
temperature. chromium content decreases below about 12%.
the corrosion resistance is severely impaired.
This structure is said t o be llsensi.tized.ll In
effect, the austenite grain boundaries a r e no
longer s t a i n l e s s s t e e l , and corrosion proceeds
rapidly. The net e f f e c t is the attack along
the austenite grain boundaries, a s shown in
Figure 4.
I n summary, the localized corrosion and
metallographic circumstances d i c t a t e the
corrosion morphology. Grain boundaries being
a zone of higher internal energy may be more
Figure 3. 500x readily corroded, referred t o a s
intergranular attack (IGA). A t elevated
Figure 3 shows intergranular corrosion of a temperatures the grain boundaries s l i p past
carbon s t e e l waterwall tube. Here the one another, a process known a s and
corrosion attack has proceeded selectively the damage c o l l e c t s along grain boundaries,
along the f e r r i t e grain boundaries. That this seen in the microstructure a s "creep damage."
is not hydrogen damage may be seen from the The d e t a i l s of the corrosion vary from
f a c t that p e a r l i t e colonies a r e s t i l l i n t a c t location t o location within the b o i l e r
within the region of intergranular corrosion depending on the local temperature and
(note encircled zone). Since t h i s damage was corrosion conditions.
noted a t the bottom of a f a i r l y large p i t
suggests the corrosion is by oxygen attack, (508) 393-3635 for metallurgical help!!!!!!!!
rather than by a pH excursion.

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