DAVID N. FRENCH, INC.

, METALLURGISTS
O N E LANCASTER ROAD
WINTER 1 9 8 6 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 VOL. 11 NO. 4
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393-3635

A VIEW FROM THE PENTHOUSE: USEFUL INFORMATION FOR THE WORLD OF BOILERS
HYDROGEN DAMAGE
Hydrogen damage h a s b e e n a p l a g u e o n t h e I n e i t h e r case t h e a t o m i c h y d r o g e n i s
b o i l e r house f o r s e v e r a l decades. There is t r a p p e d between t h e t u b e s u r f a c e a n d t h e
now c o n s i d e r a b l e i n f o r m a t i o n a n d u n d e r s t a n d - scale. Some o f t h e n a s c e n t o r a t o m i c hydro-
i n g o f how t o p r e v e n t i t . However t h e prob- gen e n t e r s t h e s t e e l , reacts w i t h t h e i r o n
l e m s t i l l o c c u r s and t h e a i l m e n t u s u a l l y c a r b i d e i n t h e s t e e l , a n d f o r m s methane:
appears abruptly with t h e f i r s t tube f a i l u r e .
I t i s more common i n o l d e r b o i l e r s t h a t h a v e
been c h e m i c a l l y c l e a n e d s e v e r a l t i m e s b u t new Atomic h y d r o g e n i s a small a t o m and c a n e a s i -
b o i l e r s a r e n o t immune. I n d e e d , i n a t l e a s t l y d i f f u s e t h r o u g h t h e s t e e l ; methane i s a
o n e case h y d r o g e n damage was o b s e r v e d i n a l a r g e m o l e c u l e and c a n n o t d i f f u s e t h r o u g h t h e
b o i l e r w i t h i n s i x months of f i r s t c o m m e r c i a l s t e e l . Methane c o l l e c t s a t g r a i n b o u n d a r i e s
start-up. and forms c r a c k s as t h e p r e s s u r e i n c r e a s e s .
Hydrogen damage i s c o n f i n e d t o t h e steam Under a m i c r o s c o p e t h e s t r u c t u r e o f hydrogen-
generating tubes, often i n t h e highest heat damaged s t e e l shows numerous f i n e c r a c k s o r
release z o n e s o f t h e f u r n a c e . I t i s a l s o f i s s u r e s a n d a l o s s o f c a r b o n , see F i g . 1.
u s u a l l y a s s o c i a t e d w i t h h e a v y , t h i c k scale
d e p o s i t s on t h e i n s i d e o f t h e t u b e . C o r r o s i o n
of t h e b o i l e r tubes proceeds under t h e s e
d e p o s i t s l i b e r a t i n g a t o m i c h y d r o g e n . Two
s c e n a r i o s e x p l a i n t h e f o r m a t i o n of hydrogen:
1. Under t h i c k , p o r o u s scales t h e water
i s t u r n e d t o steam which i n t u r n c o n c e n t r a t e s
t h e h y d r o x i d e p r e s e n t i n t h e b o i l e r water.
A s t h e pH i n c r e a s e s , t h e c o r r o s i o n r a t e o f
s t e e l a l s o i n c r e a s e s . The r e a c t i o n o f hydrox-
i d e w i t h steel forms t h e f e r r o a t e i o n and
hydrogen, thus:
2 0 ~ - + F e = Fe0; + 2H
2. Under a c i d i c c o n d i t i o n s h y d r o g e n i o n
reacts w i t h s t e e l t o f o r m f e r r o u s i r o n i o n s
and h y d r o g e n

Low pH c o n d i t i o n s c a n a r i s e from a p o o r Figure 1

c h e m i c a l c l e a n i n g . Acid i s l e f t b e h i n d ,
s a t u r a t i n g t h e porous i n t e r n a l d e p o s i t s t h a t
a r e n o t removed by t h e c l e a n i n g o p e r a t i o n .
Incomplete n e u t r a l i z a t i o n of t h e a c i d s used
l e a v e t h e d e p o s i t s i n a n a c i d i c state. Rapid
c o r r o s i o n a n d release o f h y d r o g e n f o l l o w s
when t h e u n i t i s r e s t a r t e d . T h i s w i l l e x p l a i n
t h e o f t e n s p o t t y , random n a t u r e o f t h e areas
within the boiler t h a t often characterize
t h e h y d r o g e n damage.
I n e x t r e m e cases t h e c a r b i d e p h a s e i s com-
p l e t e l y consumed a n d o n l y f e r r i t e a n d g r a i n
boundary c r a c k s r e m a i n . On a m a c r o s c a l e ,
t h e steel t u b e l o s e s both s t r e n g t h and duct-
i l i t y . F a i l u r e s are c h a r a c t e r i z e d by t h i c k
edged, b l u n t appearing f r a c t u r e s . Often a
window i s blown o u t o f t h e t u b e . The I D
s u r f a c e i s rough, wasted, and r e f l e c t s t h e
c o r r o s i o n t h a t h a s o c c u r r e d . A t t h e moment
o f r u p t u r e , any r e m a i n i n g scale i s blown o u t
 l e a v i n g t h e f r a c t u r e area r e l a t i v e l y c l e a n a n d
deposit-free. Usually t h e f i r s t s i g n t h a t a
b o i l e r s u f f e r s f r o m h y d r o g e n damage i s , i n -
deed, a f a i l u r e . There i s , however, no s u c h
t h i n g a s a l i t t l e h y d r o g e n damage.
T h e r e a r e s e v e r a l ways t o s u r v e y a b o i l e r
f o r h y d r o g e n damage. F i r s t , h o w e v e r , i t i s
desirable t o study a f a i l e d tube carefully
o v e r a l e n g t h o f 2 0 f e e t o r s o , 10-12 f e e t
e i t h e r s i d e o f t h e f a i l u r e . The s a m p l e i s
c u t o p e n a l o n g t h e membrane s o t h e f i r e s i d e
o f t h e I D o f t h e t u b e may b e viewed o v e r i t s
e n t i r e length. A l l too frequently t h e thick
internal deposits that indicate potential
h y d r o g e n damage are s p o t s no l o a r g e r t h a n a
s i l v e r d o l l a r , spaced s e v e r a l i n c h e s t o a few
f e e t a p a r t . With t h e 20 f o o t s e c t i o n a s a
g u i d e , w a l l t h i c k n e s s measurements are t a k e n
a n d t h e e x i s t e n c e o f h y d r o g e n damage c o n f i r m -
e d by m i c r o s t r u c t u r a l e x a m i n a t i o n . With t h e
e x p e c t e d morphology o f h y d r o g e n damage f o r
t h e p a r t i c u l a r b o i l e r e s t a b l i s h e d , and t h e
e x p e c t e d w a l l t h i c k n e s s measured a t t h e reg-
i o n s o f h y d r o g e n damage, t h e b o i l e r c a n b e
s u r v e y e d f o r t h e e x t e n t o f damage.
UT t h i c k n e s s g u a g e s may b e u s e d a n d a r e
u s u a l l y t h e most c o n v e n i e n t t o o l . The crown
w a l l t h i c k n e s s o f e a c h 1 0 t h o r 2 0 t h t u b e must
be measured o v e r as l o n g a d i s t a n c e as i n d i c a -
t e d by t h e 2 0 f o o t t e s t t u b e . Not a s i m p l e o r
e a s y t a s k t o d o ! Once t h e u n i t h a s b e e n
s u r v e y e d a n d t h e e x t e n t o f damage d e t e r m i n e d ,
r e p l a c e m e n t i s t h e o n l y way t o f i x t h e b o i l e r .
Boroscopic e x a m i n a t i o n s from t h e I D o f t h e t u b e
may a l s o b e p e r f o r m e d . Some of t h e f i b e r o p t i c
devices a v a i l a b l e today give e x c e l l e n t resol-
u t i o n a n d a i d i n f i n d i n g t h e most l i k e l y l o c a -
t i o n s o f h y d r o g e n damage. With t h e a d v e n t o f
m i n i a t u r e t e l e v i s i o n cameras i t i s now pos-
s i b l e t o i n s p e c t t h e i n t e r n a l s u r f a c e s of
b o i l e r t u b e s o v e r t h e i r whole l e n g t h from t h e
u p p e r waterwall h e a d e r s . S u s p e c t e d l o c a t i o n s
c a n t h e n be examined by UT a n d removed f o r
metallographic confirmation. I n general it
would b e d e s i r a b l e t o p e r f o r m s u c h a TV moni-
t o r i n g a f t e r each chemical cleaning t o a s s u r e
complete removal of a l l i n t e r n a l d e p o s i t s .
OTHERS WHO MAY WISH TO RECEIVE OUR NEWSLETTER:
NAME :
COMPANY:
1 ADDRESS:
1 TOPICS FOR CONSIDERATION :
Keeping t h e b o i l e r f r e e from t h e s e d e p o s i t s
i s t h e s u r e s t way t o p r e v e n t a r e t u r n o f t h i s
plague.
T h e r e are two r e l a t i v e l y s i m p l e t e s t s
f o r h y d r o g e n damage:
1. C u t a r i n g s e c t i o n 112'' - 314" l o n g
from t h e s u s p e c t e d l o c a t i o n . Squeeze t h e
r i n g s e c t i o n i n a v i s e w i t h t h e f i r e s i d e of
t h e t u b e a l i g n e d with t h e j a w s of t h e v i s e .
T h i s o r i e n t a t i o n w i l l p u t t h e hydrogen-dam-
a g e d r e g i o n i n t e n s i o n when s q u e e z e d . S i n c e
t h e i n t e r n a l cracks reduce d u c t i l i t y , i f
h y d r o g e n damage e x i s t s t h e r i n g w i l l b r e a k
i n a b r i t t l e f a s h i o n . The c a s i n g s i d e o f t h e
t u b e w i l l be u n a f f e c t e d and w i l l merely f l a t -
t e n . No c r a c k s o r b r i t t l e f r a c t u r e w i l l o c c u r
i n t h e a b s e n c e of h y d r o g e n damage.
2. Use a s i m i l a r r i n g s e c t i o n as d e s c r i b -
e d above and p l a c e i n b o i l i n g h y d r o c h l o r i c
a c i d f o r s e v e r a l m i n u t e s . The hydrogen-damaged
area w i l l b e a t t a c k e d more r a p i d l y t h a n s o u n d
metal. The r e s u l t w i l l b e a f u z z y g r a y , t h i n -
n e r r e g i o n w h e r e t h e damaged z o n e e x i s t s .
Upon d i s c o v e r y o f h y d r o g e n damage t h e
b o i l e r f e e d water u p s e t s t h a t c a u s e t h e c o r r o -
s i o n i n t h e f i r s t p l a c e must b e c o r r e c t e d .
Leaks i n t h e p r e b o i l e r c i r c u i t s , condenser,
f e e d w a t e r h e a t e r , e t c . , need t o b e f i x e d . Up-
grade t h e b o i l e r feedwater treatment t o a s s u r e
water o f t h e p r o p e r c h e m i s t r y a t a l l times.
Unfortunately, unless t h e s e water treatment
s t e p s a r e t a k e n , t h e h y d r o g e n damage t h a t
h a s been s o expensively r e p a i r e d i s l i k e l y
t o return.
The a d d i t i o n o f chromium t o f e r r i t i c
steels r e d u c e s t h e tendency t o hydrogen
damage. P l a i n c a r b o n s t e e l s , s i m i l a r t o
SA-210, o r SA-178 c a n b e r e p l a c e d w i t h SA-213
T-11, o r T-22. Chromium s t a b i l i z e s t h e i r o n
c a r b i d e s o t h e r e d u c t i o n t o m e t h a n e by
hydrogen d o e s n o t o c c u r as r e a d i l y . There i s ,
h o w e v e r , no known method f o r t h e r e p a i r o f
a l r e a d y damaged t u b i n g , r e p l a c e m e n t i s t h e o n l y
way. Removal o f t h e d e p o s i t s and c o r r e c t i o n
o f water c h e m i s t r y w i l l p r e v e n t f u r t h e r dam-
a g e and arrest t h e p r o c e s s , b u t n o t r e p a i r
these existing defects.
TITLE :