Corrosion Fatigue of Type 4140 High Strength Steel

H. H. L E E AND H. H. UHLIG F a t i g u e t e s t s w e r e c a r r i e d out on 4140 s t e e l heat t r e a t e d to v a r i o u s h a r d n e s s l e v e l s . Env i r o n m e n t a l e f f e c t s a r e r e p o r t e d in d r y and m o i s t a i r , a e r a t e d and d e a e r a t e d 3 pct NaC1 s o l u t i o n , and u n d e r c o n d i t i o n s of cathodic p r o t e c t i o n and of p a s s i v i t y . C r i t i c a l c o r r o s i o n r a t e s w e r e m e a s u r e d below which the e n v i r o n m e n t d o e s not affect fatigue l i f e . The r e s u l t s a r e i n t e r p r e t e d in t e r m s of e n v i r o n m e n t a l l y - i n d u c e d p l a s t i c d e f o r m a t i o n .

ALTHOUGH a r i o u s v

fatigue s t u d i e s of high s t r e n g t h s t e e l s have been r e p o r t e d , the data u s u a l l y r e f e r to a i r ; only s e l d o m a r e o t h e r e n v i r o n m e n t s m e n t i o n e d . T h o m s o n , 1 studying the fatigue b e h a v i o r of AISI 52100 and 5160 s t e e l s , p o i n t e d to the d a m a g i n g e f f e c t s of i n c l u s i o n s in the s t e e l and of m o i s t u r e in a i r . He doubted the e x i s t e n c e of a r e a l fatigue l i m i t for high s t r e n g t h s t e e l s . W a d s w o r t h 2 r e p o r t e d an i m p r o v e m e n t in the fatigue l i m i t of 0,5 p c t C s t e e l when t e s t e d in v a c u u m i n s t e a d of in a i r . Mantel e t a l . 3 r e p o r t e d that the fatigue life of high s t r e n g t h SAE 52100 s t e e l w a s s e n s i t i v e l y l o w e r e d by m o i s t u r e in a i r , n i t r o g e n and a r g o n and r e c o m m e n d e d that h u m i d i t y of the t e s t e n vironment be closely controlled. Dahlberg 4 confirmed that w a t e r v a p o r in a i r can g r e a t l y i n c r e a s e r a t e of fatigue c r a c k p r o p a g a t i o n in a high s t r e n g t h 4340 s t e e l . L i e t a l . 5 s i m i l a r l y r e p o r t e d that fatigue c r a c k growth of 0.45 p c t C, low a l l o y high s t r e n g t h s t e e l w a s a c c e l e r a t e d by m o i s t u r e in a i r o r in a r g o n , the effect of which d e c r e a s e d with f r a c t u r e t o u g h n e s s of the s t e e l . I n c r e a s e d m o i s t u r e beyond a s p e c i f i c r e l a t i v e h u m i d i t y (R.H.) of 40 pct a p p e a r e d to have no f u r t h e r d a m a g i n g e f f e c t , s i m i l a r to the effect of m o i s t u r e d e s c r i b e d by J o h n s o n and W i l l n e r 8 for high s t r e n g t h s t e e l under c o n d i t i o n s of s t a t i c loading. The l a t t e r i n v e s t i g a t o r s r e p o r t e d that the c r a c k g r o w t h r a t e i n c r e a s e s with r e l a tive h u m i d i t y , b e c o m i n g i d e n t i c a l to the r a t e in w a t e r at o r a b o v e 60 p c t R.H. Hanna e t a l . 7 in s i m i l a r s t a t i c l o a d t e s t s of high s t r e n g t h AISI 4340 and 300 M s t e e l s a l s o found m o i s t u r e in a r g o n to be d a m a g i n g , a dew point of - 5 ~ (-21~ (or r e l a t i v e h u m i d i t y of 3 pct) b e i n g s u f f i c i e n t to i n i t i a t e a c r a c k . Duquette and Uhlig s found no effect of m o i s t u r e in oxygen (93 pct R.H.) on the fatigue l i m i t of a 0,18 p c t C m i l d s t e e l (AISI 1015, R B = 77); at a p p l i e d s t r e s s e s above the f a t i g u e l i m i t , the fatigue life in m o i s t 02 w a s a c t u a l l y i n c r e a s e d o v e r that in d r y 02. To the c o n t r a r y , in a r gon at s t r e s s e s above the fatigue l i m i t , m o i s t u r e d e c r e a s e d the fatigue l i f e . F o r a m o d e r a t e s t r e n g t h AISI 1035 s t e e l (87 k s i t e n s i l e s t r e n g t h ) , M e h d i z a d e h e t a l . 9 found that a fatigue limit~ which did not e x i s t in a e r a t e d 5 pct NaCI s o l u tion, w a s o b s e r v e d when the s o l u t i o n w a s c o m p l e t e l y d e a e r a t e d . T h e s e r e s u l t s w e r e c o n f i r m e d by Duquette and Uhlig 8 for AISI 1015 m i l d s t e e l in d e a e r a t e d 3 p c t NaCI s o l u t i o n . The l a t t e r i n v e s t i g a t o r s *~ a l s o r e p o r t e d that a c r i t i c a l c o r r o s i o n r a t e e x i s t s in a q u e o u s s o l u H. H. LEE, formerly Graduate Student, Massachusetts Institute of Technology, Cambridge, Mass., is now with Inland Steel Co., South Chicago, Ill. H. H. UHLIG is Professor, Department of Metallurgy and Materials Science, M.I.T. Manuscript submitted November 2, 1971. METALLURGICAL TRANSACTIONS

t i o n s below which the fatigue l i m i t i s r e g a i n e d . It is the p u r p o s e of the p r e s e n t i n v e s t i g a t i o n to o u t line the c o r r o s i o n fatigue b e h a v i o r of high s t r e n g t h 4140 s t e e l in both m o i s t and d r y a i r , and in a e r a t e d and d e a e r a t e d 3 p c t NaC1 s o l u t i o n s for the s t e e l heat t r e a t e d to v a r i o u s h a r d n e s s l e v e l s . Included a r e the e f f e c t s of cathodic p r o t e c t i o n , the m e a s u r e m e n t of c r i t i c a l c o r r o s i o n r a t e s at v a r i o u s a p p l i e d s t r e s s e s , and a d i s c u s s i o n of m e c h a n i s m s . EXPERIMENTAL PROCEDURE

T w o Wiedemann SF-2-U reverse bend fatigue testing machines operating at 1800 cycles/min were e m ployed. The test material, as-received, was AISI 4140 3 steel in the form of -~ in. (0.95 cm) diam rod, supplied by the courtesy of Inland Steel Company. The composition of this steel is shown in Table I. For preparing specimens tested in the as-received and stress-relieved condition, bars were cut to a length of 7 in. (17.8 cm) and then stress relieved at 550~ (1020~ for 1 h in an a r g o n a t m o s p h e r e , f o l lowed by f u r n a c e cooling. The m i d s e c t i o n of the s t r e s s - r e l i e v e d b a r s w a s then m a c h i n e d to a m i n i m u m d i a m e t e r of 0.16 in. (0.406 cm) with a l in. (2.54 cm) r a d i u s of c u r v a t u r e . The m i d s e c t i o n w a s p o l i s h e d with e m e r y p a p e r s t a r t i n g with No. I and ending with 3/0. F o r s p e c i m e n s t e s t e d in the quenched and t e m p e r e d condition, the 7 in. r o d s w e r e f i r s t m a c h i n e d at the m i d s e c t i o n to a r e d u c e d d i a m e t e r of 0.18 in. (0.457 cm) on a I in. r a d i u s , followed by h e a t t r e a t m e n t at 850~ (1560~ for 45 rain in a n e u t r a l s a l t bath and then oil quenched. The r e d u c e d c e n t e r s e c t i o n s of the quenched, o r quenched and t e m p e r e d , s p e c i m e n s w e r e f u r t h e r ground or m a c h i n e d to the final d i a m e t e r of 0.16 in. S p e c i m e n s of 5 d i f f e r e n t h a r d n e s s v a l u e s w e r e p r e p a r e d ; t h e i r d e t a i l s of heat t r e a t m e n t and m e c h a n i c a l p r o p e r t i e s a r e shown in T a b l e If. P r i o r to t e s t i n g , the s p e c i m e n s w e r e d e g r e a s e d in b e n z e n e , p i c k l e d in 5 p c t n i t r i c a c i d (to a v o i d h y d r o gen pickup) for 2 min at 90~ (195~ then w a s h e d s u c c e s s i v e l y in d i s t i l l e d w a t e r , a c e t o n e and b e n z e n e , and f i n a l l y d r i e d with w a r m a i r . They w e r e m o u n t e d in the t e s t m a c h i n e with the c e n t e r s e c t i o n s u r r o u n d e d by a c y l i n d r i c a l c e l l c o n s t r u c t e d of L u c i t e p l a s t i c

Table I. Composition of AISI 4140 Steel Wt Pct C 0.41 Cr 0.99 Mo 0.16 Mn 0.81 $1 0.27 S 0.015 P 0.012 Ni 0.10 N 0.013 AI 0.044

VOLUME 3, NOVEMBER 1972-2949

Table II. Physical Properties of Heat-Treated 4140 Steel

Yield Strength, 0.2 Pct Offset, ksi

Heat Treatment

Hardness, RC

Tensile Strength, ksi

A. As-recewed, stress relieved at 550~ 1 h, furnace cooled B. Oil quenched from 850~ tempered 1 h at 625~ air cooled C. Oil quenched from 850~ tempered 1 h at 515~ air cooled D. Oil quenched from 850~ tempered 1 h at 415~ air cooled E. Oil quenched from 850~

20 + 1 28 -+ 1

96 125

115 141

37 -+ 1

164

175

44 + 1.5

204

221

w a s u s e d for t e s t s e m p l o y i n g c o n s t a n t anodic c u r r e n t in d e a e r a t e d 3 pct NaC1 solution. B e f o r e any of the t e s t s in d e a e r a t e d s o l u t i o n s w e r e begun, m o u n t e d s p e c i m e n s w e r e a l l o w e d to r e m a i n in the r e c i r c u l a t i n g s o l u t i o n for p e r i o d s of 6 h o r m o r e in o r d e r to e l i m inate oxygen that w a s i n t r o d u c e d into the s y s t e m d u r ing mounting. All t e s t s w e r e c a r r i e d out in a c o n s t a n t t e m p e r a t u r e r o o m m a i n t a i n e d at 25 ~ I~ A p p l i e d s t r e s s w a s d e t e r m i n e d by m e a s u r i n g m a x i m u m d e f l e c t i o n of the o s c i l l a t i n g s p e c i m e n u s i n g a c a t h e t o m e t e r in conjunction with s t r o b o s c o p i c l i g h t . The m a x i m u m a p p l i e d s t r e s s w a s then c a l c u l a t e d in a c c o r d with the equation: a
=

1.25

1065T

52 -+ 1.5

242

315

which h e r m e t i c a l l y s e a l e d the r e d u c e d s e c t i o n of the s p e c i m e n m a k i n g use of r u b b e r - r i n g g a s k e t s c o m p r e s s e d b y t h r e a d e d c a p s . A s k e t c h of the m a i n f e a t u r e s of the t e s t c e l l and of the r e c i r c u l a t i n g s y s t e m f o r a q u e o u s e n v i r o n m e n t s w a s d e p i c t e d in an e a r l i e r p a p e r , s M a j o r m o d i f i c a t i o n s u s e d in the p r e s e n t i n v e s 1 9 t i g a t i o n i n c l u d e d the u s e of r u b b e r - w a l l s i d e s -~ m. t h i c k , and an i n c r e a s e in o u t e r d i a m e t e r of the c e l l f r o m 1.5 to 2 in. to a c c o m m o d a t e the g r e a t e r r e q u i r e d d e f l e c t i o n of high s t r e n g t h s t e e l s p e c i m e n s . E x t r a p r e c a u t i o n w a s taken a g a i n s t oxygen e n t e r i n g the cell at the a l t e r n a t e l y s t r e s s e d r u b b e r - r i n g g a s k e t s by c o n t i n u o u s l y p a s s i n g p u r i f i e d n i t r o g e n t h r o u g h two s m a l l a d d i t i o n a l L u c i t e c h a m b e r s m o u n t e d at both e n d s of the c e l l o u t s i d e the t h r e a d e d end c a p s . T h i s d e s i g n r e d u c e d the p o s s i b i l i t y of a i r diffusing along the r u b b e r ring-specimen interface causing contamination. F i l t e r e d a i r w a s d r i e d by p a s s i n g it t h r o u g h cold t r a p s s u r r o u n d e d by s o l i d CO2-acetone. A i r of s p e cific r e l a t i v e h u m i d i t y w a s o b t a i n e d by p a s s i n g it t h r o u g h two 6 - l i t e r b o t t l e s in s e r i e s , the f i r s t c o n t a i n ing a d i l u t e solution of a given s a l t and the s e c o n d containing a s a t u r a t e d s o l u t i o n of the s a m e s a l t at a c o n s t a n t t e m p e r a t u r e of 25~ S a t u r a t e d s o l u t i o n s of CaC12, NaNO2, m i x t u r e s of NH4C1 and KNO~, NaC1, (NH4)2SO4, and KNOs p r o v i d e d r e l a t i v e h u m i d i t i e s of 31, 65, 71, 75, 81, and 93 pct, r e s p e c t i v e l y , a s c h e c k e d with a d r y - w e t bulb t h e r m o m e t e r c o m b i n a t i o n . F o r d e a e r a t i o n of a q u e o u s s o l u t i o n s , n i t r o g e n p u r i f i e d o v e r c o p p e r t u r n i n g s at 450~ w a s b u b b l e d t h r o u g h the s o l u t i o n for s e v e r a l h o u r s ; t h i s g a s w a s a l s o u s e d to r e c i r c u l a t e the d e a e r a t e d s o l u t i o n by m e a n s of a g a s lift p u m p . A s a f u r t h e r p r e c a u t i o n a g a i n s t oxygen c o n t a m i n a t i o n , a d e a c t i v a t o r containing a l a r g e a r e a of i r o n foil w a s i n s e r t e d j u s t b e f o r e the t e s t c e l l . Tests under potentiostatic control employed a Wenking p o t e n t i o s t a t . F o r t h e s e m e a s u r e m e n t s , the t e s t cell w a s m o d i f i e d to include a p l a t i n u m m e s h counter e l e c t r o d e which l i n e d the i n n e r w a l l of the L u c i t e c e l l , and a g a s k e t - s e a l e d g l a s s Luggin c a p i l l a r y m a d e c o n t a c t with a s a t u r a t e d c a l o m e l r e f e r e n c e e l e c t r o d e . A f l e x i b l e 2.5 m m d i a m Tygon tube f i l l e d with e l e c t r o l y t e s e r v e d a s a s a l t b r i d g e . The g l a s s c a p i l l a r y within the c e l l w a s a d j u s t e d to a u n i f o r m d i s t a n c e of 2 m m f r o m the m i n i m u m r a d i u s of the s p e c i m e n s u r f a c e . P o t e n t i a l s a r e r e p o r t e d on the s t a n d a r d h y d r o gen s c a l e (S.H.E.) a s s u m i n g 0.242 V for the s a t u r a t e d c a l o m e l e l e c t r o d e and o m i t t i n g a s m a l l liquid junction c o r r e c t i o n . A s i m i l a r c e l l without r e f e r e n c e e l e c t r o d e 2950-VOLUME 3, NOVEMBER 1972

w h e r e a is the m a x i m u m a p p l i e d s t r e s s in p s i at the m i d s e c t i o n of the s p e c i m e n s u r f a c e and 8T i s the t o t a l d e f l e c t i o n in i n c h e s at the end of the s p e c i m e n . The c o e f f i c i e n t w a s d e r i v e d by i n t e g r a t i n g the bending m o m e n t c u r v e s for the p r e s e n t s p e c i m e n d i m e n s i o n s u s i n g a Y o u n g ' s m o d u l u s of 29.0 x 106 p s i . RESULTS Gaseous Environments The S-N c u r v e s in d r y a i r for s t e e l of h a r d n e s s v a l u e s RC 20 to 52 a r e shown in F i g s . 1 to 5. A d e f i nite fatigue l i m i t e x i s t s for e a c h h a r d n e s s l e v e l , i n cluding the h i g h e s t s t r e n g t h m a t e r i a l . P a r a l l e l to data for s t e e l s in g e n e r a l , the fatigue l i m i t i s a p p r o x i m a t e l y o n e - h a l f the t e n s i l e s t r e n g t h , F i g . 6. In a i r of 93 pct r e l a t i v e h u m i d i t y (R.H.), s t e e l s of R c 20 and 28 show no effect of m o i s t u r e , the fatigue l i m i t s b e i n g the s a m e a s in d r y a i r . T h i s i s in a c c o r d with d a t a r e p o r t e d p r e v i o u s l y by Duquette and Uhlig f o r AISI 1015 s t e e l . H o w e v e r , for h i g h e r h a r d n e s s v a l u e s , at and a b o v e RC 37, m o i s t u r e s h o r t e n s the o b s e r v e d fatigue l i f e in a i r , the p e r c e n t a g e effect b e i n g g r e a t e r the h i g h e r the h a r d n e s s and c o r r e s p o n d i n g t e n s i l e s t r e n g t h of the s t e e l . T h i s r e s u l t c o n f i r m s the c o n c l u s i o n of

80
t a~ - \ k

,,,,I

l I,,,

70

2o~ =~ ~
9X 9 *oez~ o A

o 9 A 9

Dry Air Air 9 3 % R H Deaerated3% NoCI Aerated 3% NaCI

60

U? W CE O3

o4

50

40

50-IO S

I I i wtlll I0 6

I I I lllll

I07 FAILURE

CYCLES TO

Fig. 1--Effect of moisture in a i r and of dissolved oxygen in 3 pct NaC1 on fatigue life of 4140 steel, RC 20, 25~ {arrows mean no failure). METALLURGICAL TRANSACTIONS

100

I I I III I

I I 1 III

15(3 120 I10

-

, ,i,,,, I

~l,ll,

Ill,~,

90

' ~ Noo~
o 0
0 ~ 0

o Dry Air 9 Air, 93% R.H,

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\o ~ - Dry Air
9 ~ -

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106

I I
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8070i i t i lllll I I

A AAerated 3 N NaCI

CYCLES TO FAILURE Fig. 2--Fatigue life of 4140 steel, R C 28, in moist and dry air, 25~

I 9 i,,I

I I IIIIII

I04

I05

IOs

I0 r

CYCLES TO FAILURE
115
I I lll~ll I ~ I 1111111 I

I lIIlll I

o
105
\ 9

Fig. 4--Fatigue life of 4140 steel, RC 44, in moist and dry air, and in aerated 3 pct NaC1, 25~

o
~ o "~o #r

1701
Dry Air
o-,-

, i lll,ll I

I ' ''"" I

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95-.I 85
--

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9

9
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75
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65 CO
-

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55

--

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t I i tiiltl I I I IIIlll I I I IIIIll

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9 9 9 \~*-- Aerated 3~ 9

Air, 93~

RH

--

104

105
CYCLES TO

106
FAILURE

IOT 9

~aCl

~9
IL,I IO6 t , l,,lJ t,.. IOT

Fig. 3--Fatigue life of 4140 s t e e l , RC 37, in m o i s t and d r y a i r ,

and in aerated 3 pct NaC1, 25~ Li e t a l . 5 that the effect of m o i s t u r e on fatigue life is l e s s the higher the f r a c t u r e t o u g h n e s s of the s t e e l . V a l u e s of fatigue s t r e n g t h at 107 c y c l e s in a i r of 93 pct R.H. a r e a l s o shown in Fig. 6. The effect of r e l a tive humidity on fatigue life of RC 52 s p e c i m e n s s t r e s s e d at 90 pct of the fatigue l i m i t in d r y a i r is shown in Fig. 7. Although g r e a t e r s c a t t e r is o b s e r v e d for high s t r e n g t h s p e c i m e n s , t h e r e is a r e l a t i v e l y s h a r p t r a n s i t i o n to no f a i l u r e at >107 c y c l e s below 65 pct R.H. This c r i t i c a l value of R.H. is p r o b a b l y not a fixed value, but is higher the lower the applied s t r e s s , a c c o u n t i n g for no effect of humidity at all for lower s t r e n g t h s t e e l s (Pc 20 and 28). In c o n t r a s t to a e r a t e d aqueous e n v i r o n m e n t s , no v i s i b l e r u s t a p p e a r e d on the s u r f a c e of s p e c i m e n s exposed to m o i s t a i r at any t i m e d u r i n g the test period. In o r d e r to d e t e r m i n e the r e l a t i v e i m p o r t a n c e of
METALLURGICAL TRANSACTIONS

IOC IO4

, , ,ll,,,I IOs

I9149

CYCLES TO FAILURE Fig. 5--Fatigue life of 4140 steel, RC 52, in moist and dry air, and in aerated 3 pct NaCI, 25~ oxygen c o m p a r e d to m o i s t u r e , t e s t s w e r e c a r r i e d out on RC 52 s p e c i m e n s in p u r i f i e d a r g o n at 93 pct R.H., Fig. 8. Within the u s u a l s c a t t e r of r e s u l t s for high s t r e n g t h s p e c i m e n s , t h e r e is no obvious d i f f e r e n c e b e tween r e s u l t s in a r g o n or in a i r at the s a m e m o i s t u r e content, s u g g e s t i n g that m o i s t u r e alone is damaging. However, s u b s e q u e n t r e s u l t s for RC 52 s p e c i m e n s s t r e s s e d at 141 k s i and cathodically p r o t e c t e d in a e r ated 3 pct NaC1 solution showed a longer life than in m o i s t a i r by a factor of 100. This r e s u l t s u g g e s t s that t r a c e s of oxygen a d s o r b e d i n i t i a l l y on the t e s t s p e c i m e n s and not r e m o v e d by gas flow d u r i n g the t e s t s
VOLUME 3, NOVEMBER 1972-2951

35o I
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Fig. 7--Effect of relative humidity of a i r on fatigue life of 4140 steel, R C 52, s t r e s s e d at 138 ksi, 25~

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ENGTH

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IN 95~176 AIR R.H.

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HARDNESS, ROCKWELL C
Fig. 6--Tensile strength, yield strength, fatigue limit in dry air, and fatigue strength at 107 cycles in 93 pct R.H. air, of 4140 s t e e l heat t r e a t e d to various h a r d n e s s values.

150 120 llO-IOOo~ '

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shortened the fatigue life in moist argon. For equivalent specimens in 3 pct NaCI solution, adsorbed O2 is automatically eliminated at the outset by chemical r e duction during external cathodic polarization. Results for RC 52 specimens were supplemented by parallel data on RC 44 specimens stressed at 90 ksi. Specimens failed at 2.3 to 3.5 x 108 cycles in purified argon of 93 R.H., but uniformly survived 107 cycles in d e a e r ated H~O or deaerated 3 pct NaC1 solution. Aqueous Environments In aerated 3 pct NaC1 solution, fatigue life, as expected, is very much reduced for steels of RC 20 to 52, Figs. 1, 3 to 5. Life, in general, lies below that observed in air of 93 pct R.H. Rust appeared, particularly at the reduced c r o s s section of the test specimens, which was localized at regions 180 deg apart c o r r e sponding to highest s t r e s s during r e v e r s e bending. When 3 pct NaC1 was deaerated with purified nitrogen, Duquette and Uhlig 8 found that the usual air fatigue limit of AISI 1015 steel was regained. Similar results are presently found for 4140 steel of RC 20 as shown in Fig. 1. Spot checks made on steels of RC 37 and 44, s t r e s s e d to 90 pct of their fatigue limits in dry air, showed that they also resisted failure in deaerated 3 pct NaC1 for >107 cycles. Specimens of RC 52, how2952-VOLUME 3, NOVEMBER 1972

io

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CYCLES TO FAILURE
Fig. 8--Effect of moist a i r and m o i s t argon on fatigue life of 4140 steel, R C 52, 25~

ever, failed short of 107 cycles in several repeat runs. Duquette and Uhlig, ~~ confirming r e s u l t s of Radd, Crowder, and Wolfe, u reported that the normal fatigue limit of 1015 steel is regained in aerated 3 pct NaC1 solution when sufficient NaOH is added to bring the final pH to at least 12. It was of interest to determine whether similar results are found in high strength steels. Tests were c a r r i e d out in aerated 3 pct NaC1, pH 12, with specimens s t r e s s e d to 90 pct of their fatigue limits in dry air (82 pct in the case of RC 44). Steels of RC 20, 37, and 44 (2 specimens each), p a r a l leling previously reported results for mild steel, did not fail within the maximum test period of 107 cycles. Four specimens of RC 52, however, failed within 7 x 104 to 2.4 x 108 cycles, two of which failed at the rubMETALLURGICAL TRANSACTIONS

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CYCLES TO FAILURE Fig. 9--Effect of applied potential of 4140 steel, R C 20, s t r e s s e d above and below the fatigue limit, on fatigue life in a e r a t e d 3 pet NaC1, 25~

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Fig. 10--Effect of applied potential of 4140 steel, R C 37, s t r e s s e d above and below the fatigue limit, on fatigue life in a e r a t e d 3 pct NaC1, 25~
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b e r - s e a l g a s k e t s of the t e s t cell where l o c a l i z e d c o r r o s i o n had initiated, r a t h e r than at the r e d u c e d section of the t e s t specimen where s t r e s s is highest. All s p e c imens a f t e r t e s t s in alkaline 3 pct NaC1 solution w e r e r e l a t i v e l y free of r u s t , but with some evidence of r a n dom pitting over the specimen s u r f a c e , accompanied by c r e v i c e c o r r o s i o n at the r u b b e r g a s k e t s . Significantly, pitted s p e c i m e n s did not n e c e s s a r i l y fail by fatigue in this p a r t i c u l a r aqueous environment. Effect of Cathodic P r o t e c t i o n Specimens of RC 20 steel cathodically p r o t e c t e d in a e r a t e d 3 pct NaC1 solution w e r e s t r e s s e d a p p r o x i m a t e l y 10 pct above and 10 pct below the fatigue l i m i t . T e s t s w e r e run to failure maintaining the specimen by means of a potentiostat at a s e r i e s of constant potent i a l s with r e f e r e n c e to a s a t u r a t e d calomel e l e c t r o d e . As the potential was made m o r e active ( g r e a t e r c a thodic c u r r e n t ) , fatigue life i n c r e a s e d a s shown in Fig. 9. At an applied s t r e s s of 53 k s i (below the fatigue limit) f a i l u r e did not occur within >107 cycles at and below --0.48 V (S.H.E.). At 65 k s i (above the fatigue limit) maximum life (4.7 x lO s cycles) was o b s e r v e d at and below the s a m e a p p r o x i m a t e potential. In other w o r d s , the specific maximum potential to achieve optimum cathodic protection was not s e n s i t i v e to applied s t r e s s . Maximum life in the l a t t e r instance was the s a m e a s that observed at the s a m e s t r e s s level in d e a e r a t e d 3 pct NaC1 solution without applied potential. In the above t e s t s , p o l a r i z e d p o t e n t i a l s m o r e active than - 0 . 9 V (S.H.E.) r e s u l t e d in a distinct odor of gaseous chlorine produced at the anode inside the test cell. Although d i s s o l v e d chlorine did not a p p e a r to a f fect the r e s u l t s , i t s formation with accompanying s u s pected c o r r o s i o n of the Pt anode was avoided by using 0.5 N NasSO4 for the most active potentials and c o r r e sponding highest c u r r e n t s through the cell. Fatigue life in sulfate solutions fell on the line r e p r e s e n t i n g
METALLURGICAL TRANSACTIONS

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Fig. l l - - E f f e c t of applied potential of 4140 steel, R C 52, s t r e s s e d at 141 ksi (below the fatigue limit) on fatigue life in a e r a t e d 3 pct NaC1 (A) and a e r a t e d 0.5 N Na2SO4 (4x), 25~

data for 3 pet NaC1, confirming that f r e e chlorine had no effect on the r e p o r t e d v a l u e s . S i m i l a r r e s u l t s for RC 37 steel a r e shown in Fig. 10 at applied s t r e s s e s 10 pct above and 10 pct below the fatigue limit for which a c r i t i c a l potential of -0.48 V i s o b s e r v e d . F o r RC 44 s p e c i m e n s , t e s t s w e r e c a r r i e d out only at an applied s t r e s s 18 pct below the fatigue l i m i t , leading to r e s u l t s like those depicted in Fig. 10 and to a c r i t i c a l potential between -0.47 and -0.49 V, consistent with the p r e v i o u s l y o b s e r v e d potentials for RC 20 and 37 s t e e l s . F o r RC 52 s p e c i m e n s , t e s t s at an applied s t r e s s of 141 k s i (90 pct of the fatigue limit) showed i n c r e a s i n g life for m o r e active applied potentials, but with m a x i mum life never reaching 107 c y c l e s , Fig. 11. Instead,
VOLUME 3, NOVEMBER 1972-2953

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Fig. 12--Effectof appliedanodic current densityon fatigue life of 4140 steel, RC20, stressed at two values belowthe fatigue limit, in deaerated3 pct NaCI, 25~ (Insert shows expanded scale for low current densities.) a m a x i m u m life of 7 x 10 s c y c l e s w a s o b s e r v e d in the p o t e n t i a l r a n g e - 0 . 5 5 to - 0 . 8 5 V b e i n g a l m o s t 100 t i m e s the life at the c o r r o s i o n p o t e n t i a l . At s t i l l m o r e a c t i v e p o t e n t i a l s , l i f e a g a i n d e c r e a s e d , r e a c h i n g about 105 c y c l e s at a p o t e n t i a l o f - 1 . 2 5 V. At the l a t t e r p o t e n t i a l , h y d r o g e n w a s v i s i b l y e v o l v e d at the s p e c i m e n s u r f a c e . Although h y d r o g e n evolution had no effect on fatigue l i f e of m i l d s t e e l o r of l o w e r s t r e n g t h 4140 s t e e l s , it i s not s u r p r i s i n g that it should a f f e c t s t e e l of the high s t r e n g t h l e v e l r e p r e s e n t e d by a h a r d n e s s of RC 52. Some of the high s t r e n g t h s p e c i m e n s f a i l e d at the r u b b e r g a s k e t s r a t h e r than at the r e d u c e d s e c t i o n of the test specimen where stress is highest, probably accounted for by c r e v i c e c o r r o s i o n of the s p e c i m e n s u r f a c e e l e c t r i c a l l y s h i e l d e d f r o m the cathodic c u r r e n t . T e s t s in 0.5 N Na2SO4 l e d to r e s u l t s s i m i l a r to t h o s e obtained for 3 pct NaC1 solution, a g a i n s u p p o r t i n g the view that d i s s o l v e d c h l o r i n e did not c a u s e s h o r t e r l i f e of s p e c i m e n s c a t h o d i c a l l y p r o t e c t e d at the m o r e a c tive potentials. At a l o w e r a p p l i e d s t r e s s of 100 k s i (65 p c t of the fatigue l i m i t ) c a t h o d i c a l l y p r o t e c t e d RC 52 s p e c i m e n s in a e r a t e d 3 pct NaC1 now r e s i s t e d f a i l u r e for >107 c y c l e s at or below about - 0 . 5 V (S.H.E.) (data not shown) and life did not d e c r e a s e at the m o s t a c t i v e p o t e n t i a l s (-0.5 to - 1 . 5 6 V), c o n t r a r y to the s i t u a t i o n for s p e c i m e n s s t r e s s e d at 141 k s i . C o n s i d e r i n g the s c a t t e r of r e s u l t s for s p e c i m e n s at t h i s h a r d n e s s l e v e l , the o b s e r v e d v a l u e of m a x i m u m p o t e n t i a l for cathodic p r o t e c t i o n i s c o n s i s t e n t with the v a l u e s obtained p r e viously for lower strength material. 2954-VOLUME 3, NOVEMBER 1972

CYCLES

TO

FAILURE

Fig. 13--Effect of applied anodic current density on fatigue life of 4140 steel, R C 44, s t r e s s e d at 90 ksi (below the fatigue limit) in deaerated 3 pct NaC1, 25~ Critical Corrosion Rates As shown by Duquette and Uhlig,I~ a critical corrosion rate exists below which the aqueous environment no longer affects fatigue life at stresses below the fatigue limit. These rates were determined in deaerated 3 pct NaC1 solution by measuring the fatigue life for various constant applied anodic current densities. Measured current densities were then translated into corrosion rates employing Faraday's law such that 0.40 pA/cm2 = I mg/dm2/day (todd) corresponding to Fe ~ Fe+ + 2e'. For RC 20 specimens, measurements + were carried out at two stress levels, i.e., 52 and 40 ksi (about I0 and 30 pct below the fatigue limit respectively). The data of Fig. 12 show that the critical corrosion rates are about the same (2.0 to 2.5 ~A/cm 2 or 5.0 to 6.3 mdd) at both values of applied stress within experimental variations of the test. In similar measurements on 1015 steel, Duquette and UhligI~ reported a value of 2.0 pA/cm2 (5 todd). For RC 37 specimens stressed at 82 ksi (about I0 pct below the fatigue limit) (data not shown) and for RC 44 specimens stressed at 90 ksi (about 18 pct below the fatigue limit) the presently obtained critical values are 2.0 and 2.8 pA/cm2 or 5.0 and 7.0 todd respectively, Fig. 13. Parallel tests for RC 52 specimens were not carried out because of the characteristicallyshort fatigue life of this material in deaerated 3 pct NaCI. The average critical current density for 4140 steel of RC 20 to 44 is 2.3 0.5 ~A/cm2 or 5.8 1.3 mdd. At current densities above approximately 30 #A/cm2 (>75 todd) fatigue life for hardness levels RC 20 to 44 approaches a constant value. Both the critical corroM T L U GC L T A S C I N EAL R I A R N A TO S

sion r a t e below which fatigue life in 3 pct NaC1 s o l u tion a t t a i n s >10 ~ c y c l e s , and the upper c o r r o s i o n r a t e above which fatigue life b e c o m e s constant a r e l a r g e l y independent of e i t h e r applied s t r e s s or t e n s i l e s t r e n g t h of the s t e e l . Although c r i t i c a l c o r r o s i o n r a t e s for 4140 steel a r e independent of heat t r e a t m e n t and applied s t r e s s , the c o m p a r a b l e c r i t i c a l r a t e s for m e t a l s other than steel can be quite d i f f e r e n t . F o r e x a m p l e , the c u r v e for the fatigue life of OFHC copper s t r e s s e d a t 16.5 ksi plotted a g a i n s t anodic c u r r e n t d e n s i t y in d e a e r a t e d 3 pct NaC1 shows a c r i t i c a l c u r r e n t d e n s i t y for no f a i l u r e at 107 c y c l e s equal to 100 p A / c m z (285 todd). This value is c o n s i d e r a b l y higher than that for s t e e l , and it is a l s o higher than the n o r m a l c o r r o s i o n r a t e of copp e r in a e r a t e d f r e s h or s a l i n e s o l u t i o n s (4 to 15 mdd), c o n s i s t e n t with the well known r e s i s t a n c e of copper to c o r r o s i o n fatigue. ~2 Effect of P a s s i v e F i l m A few m e a s u r e m e n t s w e r e c a r r i e d out to d e t e r m i n e the effect of the p a s s i v e film on fatigue life of RC 20 s p e c i m e n s . S p e c i m e n s w e r e a n o d i c a l l y p o l a r i z e d in a e r a t e d 0.5 N Na2SO4 solution to a potential of 0.84 V (S.H.E.) which, in a c c o r d with p r e v i o u s l y d e t e r m i n e d p o t e n t i o s t a t i c p o l a r i z a t i o n c u r v e s , l i e s within the p a s sive r a n g e (0.5 to 1.4 V). To r e d u c e the l a r g e total c u r r e n t r e q u i r e d to achieve p a s s i v i t y , the s p e c i m e n s u r f a c e , except for the r e d u c e d s e c t i o n , was c o v e r e d with v i n y l tape. F a t i g u e life at an applied s t r e s s below the fatigue l i m i t was c o m p a r a b l e to the life of n o n p a s sive s p e c i m e n s , a s data show in Table III. Hence the p r e s e n c e of a p a s s i v e film is a p p a r e n t l y not i m p o r t a n t in d e t e r m i n i n g fatigue life. Cowley e t a l . , z3 on the other hand, r e p o r t e d the s u c c e s s f u l anodic p r o t e c t i o n of 0.08 and 0.19 pct C s t e e l s fatigued in 10 pct NH4NO3 solution, the s t e e l s when p r o t e c t e d achieving a fatigue l i m i t equal to or g r e a t e r than that in a i r . The s a m e s t e e l s when not a n o d i c a l l y p r o t e c t e d exhibited m u c h s h o r t e r l i v e s . A few additional r e s u l t s shown in T a b l e III d e m o n s t r a t e that anodic p r o t e c t i o n of 4140 s t e e l , RC 20, can s i m i l a r l y be achieved in l0 pct NaNO3 s o l u tion, but this p r o t e c t i o n is o b s e r v e d whether or not the s t e e l i s p o l a r i z e d into the p a s s i v e r e g i o n . As d i s c u s s e d l a t e r , the d e t e r m i n i n g factor a p p e a r s to be not the p r e s e n c e or a b s e n c e of a p a s s i v e f i l m , but r a t h e r the r e l a t i v e c o r r o s i o n r a t e s in a given aqueous environment. DISCUSSION Gaseous Environments The present data show that fatigue limits exist for high strength 4140 steel in dry air, and that the values approximate one-half the tensile strength even at the highest hardness value. In presence of moisture, however, the fatigue life decreases for steel of R C 37 or higher. This deleterious effect of moisture confirms earlier statements t'a-5 to the effect that moisture is a d a m a g i n g constituent of o r d i n a r y a t m o s p h e r e s . It a l s o e x p l a i n s the data p r e v i o u s l y r e p o r t e d b y Garwood e! al. 14 for 4140 s t e e l indicating that the fatigue l i m i t is l i n e a r with h a r d n e s s value up to RC 40 but l e v e l s off or d e c r e a s e s at higher h a r d n e s s v a l u e s , a c c o m p a n i e d METALLURGICALTRANSACTIONS

Table III. Effect of Passive Film on Fatigue Life of 4140 Steel (R e 20), 25~

Applied Stress, ksi 53.0 53.0 53.5 53,0 53,5 53.0 53.5

Electrolyte 0.5 _NNa2SO4 0.5 _NNa~SO4 0,5 _NNa~ SO4 0.5 _NNa~SO4 0 5 N Na~ SOn 10 pet NaNO3 10 pet NaNOa

Controlled Potential, V, (S.H,E.) +0,84 (passive) +0.84 (passive) None (not passve) None (not passive) None (not passive) *0,84 (passive) None (not passive)

Fatigue Life, Cycles 4.7 X l0 s 4,9 X lOs 4,5 X 10s 4.0 X I0 ~ 3.4 X l 0 s >107 (2 spec.) >107 (2 spot,)

by lack of r e p r o d u c i b l e b e h a v i o r . T h e s e effects w e r e explained as p r o b a b l y due to q u e n c h e d - i n s t r e s s e s , but it i s m o r e likely, in view of the p r e s e n t r e s u l t s , that high h u m i d i t y was the d i s t u r b i n g factor in t h e i r t e s t s c a r r i e d out in an u n c o n t r o l l e d e n v i r o n m e n t . J o h n s o n and W i l l n e r 6 in s t a t i c s t r e s s t e s t s of 0.42 pct C, H-11 steel at r o o m t e m p e r a t u r e found a constant r a t e of c r a c k growth in a r g o n above about 60 pct R.H. They a s c r i b e this b e h a v i o r to the e q u i l i b r i u m c o n d e n s a tion of w a t e r within the c a p i l l a r y f o r m e d at the s m a l l r a d i u s of the c r a c k tip. The s a m e explanation is not likely for the 65 pct R.H. m e a s u r e d in p r e s e n t t e s t s on RC 52 s p e c i m e n s above which f a i l u r e i s short and below which f a i l u r e does not o c c u r within >10 T c y c l e s , Fig. 7. F o r one r e a s o n , life of RC 52 s p e c i m e n s i s the s a m e in a i r or a r g o n of 93 pct R.H. over a r a n g e of applied s t r e s s e s , Fig. 8. T h i s identical b e h a v i o r is not expected in the event that w a t e r were to condense in the p r e s e n c e of a i r , on the one hand, and of an i n e r t gas on the other. F u r t h e r m o r e , life is the s a m e for RC 20 and RC 28 s p e c i m e n s exposed to e i t h e r dry or 93 pct R.H. a i r ; w e r e w a t e r to condense within the i n c i p i e n t or growing c r a c k s , fatigue life would be m u c h s h o r t e r in m o i s t a i r . In fact, life of 1015 steel at s t r e s s e s above the fatigue l i m i t i s found to be longer in m o i s t than in dry oxygenfl F i n a l l y , RC 44 s p e c i m e n s s t r e s s e d at 90 ksi w e r e found to fail in p u r i f i e d argon of 93 pct R.H. w h e r e a s in d e a e r a t e d w a t e r no f a i l u r e o c c u r r e d in >107 c y c l e s . T e m p e r a t u r e of the t e s t s p e c i m e n does not e n t e r the explanation, b e c a u s e a t h e r m o c o u p l e spot welded to RC 52 s p e c i m e n s c y c l i c a l l y s t r e s s e d in a i r at 140 k s i showed a r i s e in t e m p e r a t u r e of no m o r e than 0.6~ Since dry a i r is l e s s damaging to fatigue life of high s t r e n g t h s t e e l s than is m o i s t a i r (<100 pct R.H.), and w a t e r f r e e of d i s s o l v e d oxygen is a l s o found to be l e s s d a m a g i n g than m o i s t a i r , the c o m b i n e d a d s o r p t i o n of H20 and O2 is a p p a r e n t l y n e c e s s a r y to account for the o b s e r v e d d e c r e a s e of fatigue life in m o i s t a i r and in m o i s t a r g o n . In m o i s t g a s e s , when c o n d e n s a t i o n of w a t e r i s avoided, e.g. by avoiding t e m p e r a t u r e f l u c t u a t i o n s , a continuing c o r r o s i o n r e a c t i o n does not take place (hence t h e r e is no v i s i b l e r u s t in any length of t i m e ) c o n t r a r y to the situation in liquid water which acts a s an e l e c t r o l y t e allowing the c o r r o s i o n r e a c t i o n to p r o c e e d , p a r t i c u l a r l y in p r e s e n c e of oxygen. The r e a c t i o n of s t e e l with any oxygen a d s o r b e d on the s t e e l s u r f a c e in p r e s e n c e of liquid w a t e r c o n s u m e s the oxygen (before the test is begun) in a c c o r d with: Fe + O (ads) + H20 ~ Fe(OH)e, but this r e a c t i o n is e i t h e r slow or does not happen in m o i s t g a s e s . Hence f a i l u r e VOLUME 3, NOVEMBER 1972-2955

is not o b s e r v e d within >107 cycles for RC 44 s p e c i m e n s in d e a e r a t e d 3 pct NaC1 in which the r e a c t i o n can go, but is o b s e r v e d in a r e l a t i v e l y short time in moist a i r or moist argon in which the r e a c t i o n does not go. An effect of m o i s t u r e in a i r on fatigue life beginning at RC 37 cannot be a s c r i b e d to hydrogen produced by the r e a c t i o n 3 Fe + 4 H20 ~ Fe304 + 4 H2 a s s u m i n g that the hydrogen, in turn, e n t e r s the steel and induces cracking. O b s e r v e d absence of c o r r o s i o n fatigue up to >107 c y c l e s for RC 37 and RC 44 s t e e l s totally i m m e r s e d in d e a e r a t e d H20 or 3 pct NaC1 e l i m i n a t e s this supposition. The effect of m o i s t u r e in g a s e s , on the other hand, may be a s c r i b e d to adsorption of H20 on a p p r o p r i a t e defect s i t e s on the metal s u r f a c e , the r e q u i r e d defects being produced only at sufficiently high s t r e s s e s . Water so a d s o r b e d may favor crack formation by r e ducing s u r f a c e energy, a s it does in the f r a c t u r e of g l a s s , or it may i m p a i r bond strength of s e v e r e l y s t r a i n e d iron a t o m s at the tip of a notch or c r a c k , as probably o c c u r s in the o b s e r v e d s t r e s s c o r r o s i o n cracking of high strength s t e e l s above a yield point of 180 k s i (>Rc 40) on exposure to moist a i r . Aqueous Environments Supplementing the previous discussion, lack of an effect of i n t e r s t i t i a l hydrogen on behavior of 4140 s t e e l up to and including RC 44 is c l e a r l y apparent from the cathodic p r o t e c t i o n data. Fatigue life is not affected in 3 pct NaC1 solution even at a potential of -1.05 V (S.H.E.) accompanied by hydrogen ion d i s c h a r g e on the metal surface. F o r RC 52 s p e c i m e n s s t r e s s e d at 141 k s i , however, applied potentials accompanied by inc r e a s i n g hydrogen evolution have an a p p r e c i a b l e effect at potentials m o r e active than --0.9 to -1.0 V (S.H.E.), Fig. 11. If i n t e r s t i t i a l hydrogen is the cause, as s e e m s likely, it n e v e r t h e l e s s has no o b s e r v e d effect on fatigue life of RC 52 s p e c i m e n s s t r e s s e d to only 100 k s i , even at a potential as active as -1.56 V. The damaging effect of hydrogen, t h e r e f o r e , a p p a r e n t l y i n c r e a s e s with the level of applied s t r e s s . A s i m i l a r t r e n d also a p p l i e s to the damaging effect of m o i s t u r e in g a s e s . Because of galvanic action with the b a s e m e t a l , s a c r i ficial m e t a l l i c coatings can in p r i n c i p l e g e n e r a t e h y d r o gen on the steel surface and can, t h e r e f o r e , be damaging to s t e e l s heat t r e a t e d to high h a r d n e s s . Magnesium coupled to RC 52 s t e e l in 3 pct NaC1 i l l u s t r a t e s a d a m aging combination. A cadmium coating on the s a m e s t e e l , however, would not be expected to cause damage b e c a u s e the c o r r o s i o n potential of cadmium in 3 pct NaC1 is -0.46 V (S.H.E.), which falls within the p r o t e c tive range shown in Fig. 11. Such a coating should in g e n e r a l be beneficial. A zinc coating having a c o r r e sponding potential of --0.79 V (S.H.E.) is in the range where fatigue life is optimum and hence such a coating can a l s o be p r o t e c t i v e . The potential of zinc, however, c o n t r a r y to cadmium, is in the region where an effect of hydrogen on fatigue life b e c o m e s a f a c t o r , c o n s e quently in an environment free of d i s s o l v e d oxygen (oxygen p a r t i a l l y r e a c t s with and consumes cathodic hydrogen), or containing poisons (e.g. H2S, a r s e n i c compounds) which s t i m u l a t e hydrogen a b s o r p t i o n by the s t e e l , the coating could in p r i n c i p l e cause p r e m a t u r e fatigue f a i l u r e of a h i g h - s t r e n g t h steel in water or a saline solution.
2956-VOLUME 3, NOVEMBER 1972

It should be noted that the m a x i m u m potential (-0.48 to -0.50 V, S.H.E.) for optimum cathodic p r o t e c t i o n of 4140 s t e e l of RC 20 to 44 is independent of h a r d n e s s or t e n s i l e strength of the s t e e l and is a l s o independent of applied s t r e s s . The value l i e s close to --0.53 V (S.H.E.) r e q u i r e d to p r o t e c t s t e e l , s t r e s s e d or u n s t r e s s e d , against r u s t i n g in s o i l s or n a t u r a l w a t e r s . This c o r respondence supports the view that the main function of cathodic protection is to r e d u c e the c o r r o s i o n r a t e r a t h e r than to a l t e r oxide f i l m s or the nature and amount of a d s o r b e d s p e c i e s on the s t e e l s u r f a c e . Lack of an effect of a p a s s i v e film on fatigue life as p r e s e n t l y r e p o r t e d c o n f i r m s e a r l i e r o b s e r v a t i o n s of Sp~hn 16 on 0.48 pct C s t e e l in 0.5 M Na2SO4, pH 0 to 8. His p a r a l l e l o b s e r v a t i o n s that anodic p r o t e c t i o n of v a r i o u s s t a i n l e s s s t e e l s is beneficial in 0.5 M Na2SO4 above but not below pH 4 suggest that the c o r r o s i o n r a t e of p a s s i v e or nonpassive steel is the p a r a m e t e r which d e t e r m i n e s fatigue life. The p a s s i v e c u r r e n t d e n s i t i e s for s t a i n l e s s s t e e l s , which a r e p r o p o r t i o n a l to c o r r o s i o n r a t e s , a r e t y p i c a l l y lower than for carbon s t e e l s . In addition the p a s s i v e c u r r e n t density at 0.84 V is known to be higher the lower the p r e v a i l i n g pH of the solution; it is p l a u s i b l e to a s s u m e that it exceeds the c r i t i c a l value or equivalent c r i t i c a l c o r r o s i o n r a t e for s t a i n l e s s s t e e l s below pH 4. The s a m e explanation apparently a p p l i e s to data of Table III. The m e a s u r e d p a s s i v e c u r r e n t density (30 # A / c m 2) for 4140 steel in 0.5 N Na2SO4 l i e s well above the c r i t i c a l c u r r e n t density of 2 ~ # A / c m 2 as d e s c r i b e d e a r l i e r , and hence the fatigue life is not improved by p a s s i v a t i o n . But in 10 pct NaNO3, the m e a s u r e d s t e a d y - s t a t e p a s s i v e c u r r e n t density at 0.84 V a p p r o x i m a t e s 3 p A / c m 2 which a p p r o a c h e s the value for the c r i t i c a l c u r r e n t density, and hence fatigue life is i m p r o v e d . However, 4140 s t e e l does not fail within 107 c y c l e s whether p o l a r i z e d or unp o l a r i z e d ; this r e s u l t l e a d s to the f u r t h e r conclusion that the c o r r o s i o n r a t e of unpolarized s t e e l in 10 pct NaNO3 is also the same o r d e r as the c r i t i c a l c o r r o s i o n rate. The regaining of a fatigue l i m i t for 4140 s t e e l , RC 20 to 44, in 3 pct a e r a t e d NaC1 of pH 12 is a s c r i b e d , as p r o p o s e d e a r l i e r , l~ to the low o v e r a l l c o r r o s i o n r a t e of steel in this solution which a p p r o a c h e s or falls below the c r i t i c a l c o r r o s i b n r a t e . The absence of f a tigue c r a c k s despite v i s i b l e s u r f a c e pits i n d i c a t e s that c o r r o s i o n pits acting as s t r e s s r a i s e r s may favor but a r e not n e c e s s a r y to the m e c h a n i s m of c o r r o s i o n f a tigue, c o n t r a r y to the suggestion of e a r l i e r i n v e s t i g a t o r s . 17'~8 At the highest strength l e v e l , RC 52 s p e c i mens probably fail b e c a u s e of the action of a d s o r b e d water i t s e l f , independent of the c o r r o s i o n r a t e . F o r this r e a s o n , RC 52 s p e c i m e n s fail s h o r t of 107 c y c l e s in d e a e r a t e d 3 pct NaC1 solution d e s p i t e a p r e v a i l i n g uniform c o r r o s i o n r a t e in this solution that is well b e low the c r i t i c a l r a t e as m e a s u r e d for P,C 44 and lower strength s p e c i m e n s . The apparent function of the c o r r o s i o n p r o c e s s , as d e s c r i b e d by Duquette and Uhlig, 8 is to s t i m u l a t e p l a s tic flow of the metal at a given s t r e s s level, t h e r e b y favoring formation of i n t r u s i o n s and e x t r u s i o n s which lead to fatigue c r a c k s . Surface dissolution of metal a t o m s conceivably f a v o r s p l a s t i c flow by d i s s o l v i n g p i l e d - u p dislocations at the m e t a l s u r f a c e which impede motion along slip planes, or m o r e p r o b a b l y by injecting i m p e r f e c t i o n s which aid the r e l a t i v e motion of slip
METALLURGICAL TRANSACTIONS

CONCLUSIONS
Table IV. Effect of Cathodic Protection on Fatigue Life of Previously Fatigued 4140 Steel Specimens, RC 44, Aerated 3 Pct NaCI, 25~

Apphed Stress, ks1 88 87 88

Initial Cycles, No Cathod. Prot. None 1.5 X l0 s 1.3 X l0 s

Additional Cycles with Cathod. Prot. None 107 lO 7

Cycles to Failure Cathod. Prot. Removed 1.2)< l0 s 0 91 X l0 s

Total Cycles to Failure, No Cathod. Prot. 2.9 X 10s 2.7 X 10 s 2.2 X l0 s

planes subject to cyclic s t r e s s . This p r o c e s s o c c u r s only above a c r i t i c a l c o r r o s i o n r a t e , and r e a c h e s steady state as the c o r r o s i o n r a t e i n c r e a s e s . If r e moval of only a few key a t o m s p e r cycle is r e q u i r e d , a s d e s c r i b e d e a r l i e r , '~ the c r i t i c a l r a t e should inc r e a s e with frequency of c y c l i c s t r e s s i n g , as should the upper c o r r o s i o n r a t e above which fatigue life a p p r o a c h e s a constant value. Hence the c r i t i c a l r a t e for s t e e l s equal to 5.8 mdd and the upper c o r r o s i o n r a t e equal to about 75 mdd apply s p e c i f i c a l l y to 1800 cycles/min. No induction time was p r e v i o u s l y o b s e r v e d for f a i l u r e of 1015 s t e e l , ~ the i n t r u s i o n s and e x t r u s i o n s l e a d ing to numerous fatigue c r a c k s in 3 pct NaC1 t y p i c a l l y p r o c e e d i n g d i r e c t l y from the m e t a l s u r f a c e and b e coming v i s i b l e under the m i c r o s c o p e within 4 pct of total life. T i m e s to failure for mild s t e e l , t h e r e f o r e , a r e m o s t l y a m e a s u r e of crack growth r a t e s . S i m i l a r l y , for 4140 steel of RC 20 in 3 pct NaC1, c r a c k s w e r e v i s i b l e in the e a r l y s t a g e s of cyclic s t r e s s i n g and t h e r e w e r e t y p i c a l l y many c r a c k s in addition to the m a j o r c r a c k accounting for final f a i l u r e . However, for the h a r d e r s t e e l s (Rc 44 or RC 52), having a m a r t e n s i t e or t e m p e r e d m a r t e n s i t e s t r u c t u r e , a definite induction t i m e was o b s e r v e d . No c r a c k s w e r e v i s i b l e under the m i c r o s c o p e at any magnification of n i c k e l - p l a t e d mounted s p e c i m e n s even after cyclic s t r e s s i n g for m o r e than 50 pct of total life, and only one m a j o r c r a c k , or at most two, w e r e in evidence at the time of final f a i l u r e . Apparently a c r a c k once nucleated p r o p a g a t e s a c r o s s the specimen t h i c k n e s s at a r a p i d r a t e . But even h e r e , the growth of m i c r o s c o p i c a l l y invisible nuclei, or p r e s u m a b l y the s m a l l p l a s t i c zones which grow to a size r e q u i r e d to nucleate a c r a c k , a r e influenced by the c o r r o s i o n p r o c e s s . This was demons t r a t e d with s p e c i m e n s of R C 44 s t e e l fatigued i n i t i a l l y in a e r a t e d 3 pct NaC1 to either 45 or 50 pct of total e x p e c t e d life, then cathodically p r o t e c t e d at -0.61 V (S.H.E.) for an additional l0 T c y c l e s , followed by r e moving cathodic p r o t e c t i o n and continuing cyclic s t r e s s i n g to failure. The data s u m m a r i z e d in Table IV show that total fatigue life is l a r g e l y unaffected by long i n t e r m e d i a t e cyclic s t r e s s i n g under conditions of cathodic p r o t e c t i o n . This r e s u l t means that cathodic p r o t e c t i o n , by eliminating s u r f a c e c o r r o s i o n , effectively inhibits the continuing growth of m i c r o s c o p i c a l l y invisible p l a s t i c zones to the size needed to nucleate a crack.

I) Type 4140 steel heat treated to the hardness range RC 20 to 52 has fatigue limits equal to about one-half the tensile strengths, but only in dry air. In moist air (93 pct relative humidity) fatigue life is shorter at and above RC 37. 2) In d e a e r a t e d 3 pct NaC1 solution, RC 20 s p e c i m e n s exhibit a fatigue l i m i t approximating that in a i r . Simi l a r l y , s p e c i m e n s of RC 37 and 44 s t r e s s e d below t h e i r fatigue l i m i t s r e s i s t failure for g r e a t e r than l0 T c y c l e s , but RC 52 s p e c i m e n s fail. 3) Cathodic protection is effective in a e r a t e d 3 pct NaCl solution for s t e e l s having h a r d n e s s values RC 20 to 44. F o r optimum protection, s t e e l s must be p o l a r ized below -0.49 V (S.H.E.). Steel of R C 52 at this p o tential exhibits longer life than n o r m a l , but suffers i n c r e a s i n g hydrogen damage below 1 V (S.H.E.). 4) Steels of RC 20 to 44 s t r e s s e d at 1800 c y c l e s / m i n below t h e i r fatigue l i m t s in a e r a t e d 3 pct NaCl solution show no environmental effects below a c o r r o s i o n r a t e of 5.8 mg/dm2/day (0.0011 in. penetration per y e a r ) . This c r i t i c a l r a t e is independent of h a r d n e s s or applied stress. 5) A p a s s i v e film on steel does not benefit fatigue life, the i m p o r t a n t p a r a m e t e r being the p r e v a i l i n g c o r r o s i o n r a t e either in the active or p a s s i v e s t a t e s . 6) C o n t r a r y to mild s t e e l , an induction time is obs e r v e d for nucleation of fatigue c r a c k s in RC 44 or 52 s t e e l s , and fewer c r a c k s a r e f o r m e d . Growth of inv i s i b l e nuclei to the c r i t i c a l size for failure is inhibited by cathodic protection.
ACKNOWLEDGMENT This r e s e a r c h was supported by the A m e r i c a n Iron and Steel Institute and by the Inland Steel Company to whom the authors e x p r e s s t h e i r a p p r e c i a t i o n . REFERENCES
1. R. Thomson: Trans. ASM, 1963, vol. 56, p 803. 2. N. Wadsworth: Phil. Mag., 1961, vol. 6, p. 397. 3. E. Mantel, G. Robinson, and R. Thomson: Metals Eng. Quart., 1961, vol. l, no. 3, p. 57. 4. E. Dahlberg: Trans. ASM, 1965, vol 58, p. 46. 5. C. Y. I.a, P. Talda, and R. Wei: Int. Z Fract. Mech., 1967, vol. 3, p. 29. 6. H. Johnson and A. Willner: Appl. Mater Res., Jan. 1965, p. 34. 7. G. Hanna, A. Troiano, and F. Stelgerwald: Trans. ASM, 1964, vol. 57, p. 658. 8. D. Duquette and H. Uhlig: Trans. ASM, 1968, vol. 61, p. 449. 9. P. Mehdizadeh, R. McGlasson, and J. Landers: Corroston, 1966, vol. 22, p. 325. 10. D. Duquette and H. Uhhg: Trans. ASM, 1969, vol. 62, p 839. 11. F. Radd, L. Crowder, and L. Wolfe: Corrosion, 1960, vol. 16, p. 415t. 12. H. H. Uhlig: The Role of a Critical Minimum Corrosion Rate on Fatigue Damage, Symp. on Corrosion FaUgue, Storrs, Conn., June 1971, N.A.C.E., Houston, Texas, to be published. 13. W. Cowley, F. Robinson, and J. Kerrich: Brit. Corros. J., 1968, vol. 3, p. 223. 14. M. Garwood, H. Zurburg, and M. Erickson: Interpretation of Tests and Correlation with Service, p. 1, American Sooety for Metals, Metals Park, Ohio, 1951 15. G. Hancock and H. Johnson: Trans. TMS-AIME, 1966, vol. 236, p 513. 16. H. Spahn: Metalloberflache, 1962, vol. 16, p. 369, Z. Physik. Chem. (Leipzig), 1967, vol. 234, p. 1. 17. D. McAdam, Jr. and R. Clyne: J. Res. Nat. Bur Stand., 1940, vol. 29, p. 685; with G. Ceil: Proc. ASTM, 194 I, vol. 41, p. 696. 18. B. Westcott: Corrosion Handbook, p. 578, John Wiley, New York, 1948.

METALLURGICAL TRANSACTIONS

VOLUME 3, N O V E M B E R 1 9 7 2 - 2 9 5 7