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surface science
ELSEVIER Apphed Surface Scmnce 76/77 (1994) 266-271

Grain boundary segregation of boron


in an austenitic stainless steel
Gary M Carlno *
Stainless Steel Metallurgy, Allegheny Ludlum Corporatlon, Techmcal Center, Alabama &Pactfic At.enues, Brackenrtdge,
PA 1501~, USA
(Recewed 2 August 1993. accepted for pubhcatlon 10 September 1993)

Abstract

A combination of transmission electron microscopy, field-ion microscopy, and atom-probe mlcroanalysls was used
to study grain boundary segregation of boron and its influence on the elemental distribution in the boundary region
m AISI type 304 (UNS $30400) austenltlC stainless steel Non-equlhbrlum segregation of boron is shown to prevail
with a maxamum concentration at the gram boundary and a tall of decreasing concentration away from the boundary
The effects of boron segregation on the elemental distribution of carbon, phosphorus, and chromium are also
discussed

I. I n t r o d u c t i o n environments With respect to such lntergranular


corrosion resistance, s~gnlflcant gram boundary
The solubdlty of boron m a chromium-nickel attack was observed after conducting the elec-
austemtm stainless steel is very low, with a solu- trolytic, 10% oxahc acid etch test (ASTM A 262-
bxhty less than 30 ppm at 900°C [1] In addition, 91, Practice A) [5] on a type 304 stainless steel
boron has been shown to segregate to grain with intentional boron additions In this test, pol-
boundarms and affect the lntergranular premplta- ished samples are electrolytlcally etched in oxalic
tlon behavmr [2] Investigators have shown that acid and the grain boundary attack is examined
chromium depletion in boron-containing stainless and rated using an optical microscope The oxahc
steels can result from the preopltatlon of a o d etch test is used to identify those specimens
chromium-rich borldes and borocarbldes [3,4] which are free of susceptibility to rapid lntergran-
Whde chromium m these steels Imparts corrosion ular attack, and such a test is used for acceptance
resistance, such preclp]tatlon processes can result but not for the rejection of material The etching
in a chrommm-depleted zone adjacent to the of the type 304 stainless steel with boron addi-
grain boundaries, which may be susceptible to tions produced deep grooves or ditches at the
lntergranular attack when exposed to aggressive grain boundaries, apparently indicative of grain
boundary precipitation Such an appearance is
typically indicative of chromium depletion and
the susceptibility to lntergranular corrosion
* Fax +1 412 2266452 However, these observations were contrary to

0169-4332/94/$07 00 © 1994 Elsevier Scmnce B V All rights reserved


SSDI 0 1 6 9 - 4 3 3 2 ( 9 3 ) E 0 2 6 6 - O
G M Canncl/Apphed Surface Sctence 76 / 77 (1994) 266-271 267

those results from the standard acid exposure and grain boundaries were brought to within 100
tests, ASTM A 262-91, Practice C (Huey test) and nm of the tip surface by controlled back-pohshing
A S T M A 262-91 Practice E (copper-accelerated [7]
Strauss test) lntergranular corrosion tests [5], A conventional, straight-flight-tube atom probe
which showed that the lntergranular corrosion was used at the University of Pittsburgh (Pitts-
resistance of the boron-containing alloy was not burgh, PA) for this study [8] The operating tem-
significantly different than that of conventional perature, neon pressure and V p / V D c (Vp=
type 304 stainless steel evaporation pulse voltage, VDC = standing DC
To evaluate the apparent precipitation effects voltage) during the analyses were, respectively, 60
in a type 304 stainless steel with boron addmons, K, 2 × 10 -8 Torr, and 0 15 The specimens were
transmission electron microscopy (TEM), field-ion first field-evaporated until the decorated grain
microscopy (FIM), and atom-probe microanalysls boundaries became visible in the field of view
(AP) were used in this study The high spatial Once delineated, the gram boundary image was
resolution and mass independent sensitivity of then centered over the entrance aperture of the
the A P F I M make this instrument well suited for time-of-flight mass spectrometer Many of the
grain boundary analysis The major drawback of boundaries were somewhat inclined to the needle
using this technique for grain boundary studies is axes and during field-evaporation the position of
the difficulty of Intercepting a grain boundary the needles had to be constantly readjusted to
within the small volume of material at the tip of keep the boundaries centered over the aperture
the needle specimen The pre-selectlon of speci- Depending upon the radius of curvature of the
mens by means of T E M helped to alleviate this specimen and the tip-to-screen distance, the di-
difficulty ameter of the analyzed area was approxamately
1-3 nm

2. Experimental procedure
3. Results
The grain boundary analysis was conducted on
annealed type 304 stainless steel samples (2 3 mm Optical metallography of the boron-containing
thick) from Ht 845674 (Table 1), which contained material, after electrolytic etching with oxalic acid,
0 0023 wt% boron The material was annealed at showed significant grain boundary attack and the
1093°C and the cooling rate after annealing was microstructure was classified as a Ditch Struc-
approxamately 1 6 - 2 2 ° C / s The annealed mi- ture, with one or more grains surrounded by
crostructure was examined and rated with respect ditches after etching (Fig 1) A Ditch Structure is
to ASTM A 262-91 Practice A typically evident in sensitized stainless steels, and
To prepare A P F I M samples for grain bound- lntergranular carbides are easily discerned using
ary analysis, the 2 3 mm thick material was hand- T E M on material in this condition, however, in
ground to a thickness of 0 4 mm and sheared into the boron-contaimng type 304 stainless steel,
specimen blanks (0 4 m m × 0 4 mm × 12 7 mm) T E M analysis of thin foils did not show any
The specimen needles were then prepared by a evidence of grain boundary precipitation Grain
conventional two-stage electropohshmg technique boundary precipitates were also not evident at a
[6] The specimens were examined using T E M magnification of 100 K during the T E M examina-

Table 1
Chemical composmon of Ht 845674 m wt% and at%
T304 Cr N1 Mn Mo Sl C N B P S Fe
wt% 18 14 8 16 1 58 0 45 0 38 0 045 0 040 0 0023 0 037 0 0005 bal
at% 19 21 7 65 1 58 0 26 0 75 0 207 0 158 0 0116 0 066 0 0011 bal
268 G M Cartnct /Apphed 3urface Science 76 / 77 (1994) 266-271

./x t--3 ,v---t

~ rs~., ~ " ".-.-C ~ ~ -... > 7"-- " -, ---'_~,:-. -I<o o ~

Fig I Optical micrograph of type 304 stainless steel with 23


ppm B showing grain boundary attack

tlon of the FIM samples (Fig 2a) Using the FIM,


the grain boundaries appeared decorated and
were easily discerned In the mlcrograph (Fig
2b), a grain boundary is decorated with bright
spots The bright spots along the gram boundary
have been identified as single boron atoms by
correlating an atom that produces a brtght spot m
the field-ion image with the atom that is collected
m the mass spectrometer when it is field-
evaporated The FIM observations clearly show
the extent to which the segregation is locahzed to ®
the interface (Fig 2b) Although the gram bound- Fig 2 (a) TEM micrograph of a grain boundary in type 304
aries appeared decorated, discrete grain bound- stainless steel (23 ppm B) inclined nearly perpendicular to the
specimen axis, and (b) the complementary FIM image show-
ary precipitates were not apparent in any of the ing the same grain boundary The FIM image shows the probe
FIM samples aperture in the center and the grain boundary decorated with
A total of six high-angle gram boundaries and boron atoms Arrows point to the grain boundary
one twin boundary was analyzed Boron segrega-
tion was found at all the grain boundaries ana- Table 2
lyzed, except at the twin boundary, and the gen- Analysis of grain boundaries (at% _+ o-) ~ in type 304 stainless
eral segregation behavior was essentially the same steel - Ht 845674
for all the high-angle boundaries analyzed The Sample Boron Carbon Phosphorus Chromium
results from these analyses (Table 2) show that 1 093_+024 106+_026 050_+//18 1830_+097
boron, carbon, and phosphorus are strongly seg- 2 239_+042 077_+024 069_+023 2086_+1 13
regated at the gram boundary The boundary 3 229_+029 101-+019 045_+013 1965+077
concentration refers to the concentration ob- 4 178_+028 062+017 045_+014 1757_+080
5 208_+027 089_+018 100_+019 1860+074
tained when the boundary was centered over the
6b 003+003 115+018 012_+002 1856+068
time-of-flight aperature The average composi- Aver 193_+013 088_+009 063+008 1888+038
tion shown for boundaries 1-5 was calculated by ofl 5
summing the total number of boron, carbon, The error hmlts correspond to one standard deviation de-
chromium, or phosphorus atoms and dividing by rived from the counting statistics
the total number of atoms in these boundaries b Denotes a twin boundary
G M Carmct/Apphed Surface Sctence 76/77 (1994) 266-271 269

The twin boundary composition with respect to from the boundary and allowing the boundary to
the carbon and chromium concentration was simi- move across the probe hole during evaporation of
lar to the high-angle boundaries Unlike the the tip A typical profile (Fig 3) shows that the
high-angle boundaries, however, the twin bound- boron is enriched within a thin zone (8 nm) along
ary showed only minor segregation of boron and the gram boundary The carbon is enriched at the
phosphorus grain boundary and the concentration profile de-
Several composition profiles were measured by creases to approximately the bulk alloy composi-
positioning the probe aperature a known distance tion of 0 2 0 at% adjacent to the boundary
Chromium is slightly depleted adjacent to the
boundary and reaches a maximum at the gram
boundary
5

4¸ 4. Discussion
G
3"
The material analyzed In this study showed
t~
significant grain boundary attack after perform-
gr- 2-

(a)
ing the oxalic etch test Such an appearance IS
usually indicative of grain boundary precipitation
and deteriorated lntergranular corrosion resis-
0 = : - I - - - T tance However, In this study the material pos-
10 0 10 sessed acceptable corrosion rates during A S T M
A262-91 Practice C and E intergranular corrosion
3"

/l
tests Kearns et al [9] have also reported similar
corrosion test results for type 304 stainless steel
containing 0 0003-0 0015 wt% boron Their re-
ot::: sults showed that the grain boundary attack, with
(b) respect to A S T M A262, Practice A, was directly
G
related to the boron content, and that type 304
G
O
L)
stainless steel containing 0 0015 wt% boron pos-
sessed discontinuous deep grooves along the grain
~. u m
I • I • boundaries after etching However, they also
10 0 ;0 found that the material possessed acceptable cor-
rosion resistance after performing A S T M A 262
28 Practice B and C lntergranular corrosion tests
26i The grain boundary attack that occurs during
" 24- etching of type 304 stainless steel with boron
i 22" additions may be indicative of the small zone of
(c) 20
chromium depletion ( ~ 8 nm) along the grain
18
boundary However, because this zone of deple-
tion is very narrow, the weight loss measured
12
after corrosion testing (ASTM A262-91 Practice
10 I I
C and E) may be insignificant Also because the
10 0 ll0 data indicate that the concentration perturbation
Dtstance f r o m G B ( n m )
near the boundary only reaches a minimum of 16
Fag 3 A t o m - p r o b e c o m p o s m o n p r o f i l e s f o r (a) B, (b) C, a n d
(c) C r as a f u n c h o n o f d i s t a n c e f r o m t h e g r a m b o u n d a r y T h e
at% or 15 wt% chromium, the depleted zone still
e r r o r b a r s a r e i n d i c a t i v e o f _+ o n e s t a n d a r d d e v i a t i o n o f t h e would be expected to maintain adequate corro-
stat~sncal c o u n t i n g e r r o r s sion resistance
270 G M Carmct /Apphed Surface Sctence 76/77 (1994) 266-271

Boron segregation to austenite grain bound- twin boundaries should show less segregation
aries has been shown to be mainly a non-equl- This is in agreement with the results presented in
hbrlum process [10] Non-equilibrium segregation this study on the segregation behavior of boron
can be contrasted with equilibrium segregation by (Table 2) However, segregation of carbon did not
the temperature and cooling rate dependences follow this trend and was found both at the
and by the shape of the concentration profiles high-angle boundaries and at the twin boundary
Equilibrium segregation is confined to within a With respect to the composition of the grain
few atomic layers at the boundary and the amount boundary region, a similar study on boron segre-
of segregation increases with the decrease in an- gation in type 316L stainless steel and "Mo-free
nealing temperature Considering that an atomic type 316L" stainless steel by Karlsson and Nord6n
layer is ~ 0 2 nm wide, equilibrium segregation [2] also showed that the boundary zone composi-
occurs over a zone of approximately 1 nm Non- tion was consistently different than the bulk com-
equilibrium segregation shows a wider (often sev- position The width of the boron-enriched zone
eral hundred atomic layers), smooth concentra- increased with decreasing cooling rate and in-
tion profile with a maximum at the boundary In creasing starting temperature, and the largest
this study, the boron segregation profile was amount of non-equilibrium boron segregation oc-
peaked at the gram boundary with a tail of de- curred after cooling at 13°C/s from a starting
creasing concentration over several nanometers, temperature of 1250°C Different groups of ele-
suggesting that non-equihbrlum segregation dom- ments showed markedly different concentration
inated during cooling from the annealing temper- profiles Chromium and molybdenum were de-
ature The segregation of carbon and phosphorus pleted adjacent to the grain boundary but en-
was localized to the grain boundary region, which riched at the boundary, while the segregation
suggests that both may segregate in an equlhb- behavior of boron was mainly of the non-equi-
rlum manner Segregation of sulfur probably oc- librium type, with maximum enrichment at the
curred within the grain boundary region, but col- grain boundary and a tail of decreasing concen-
lection of quantitative data on sulfur was not tration away from the boundary The type 304
possible because of the m a s s / c h a r g e overlap of stainless steel analyzed in the present study con-
sulfur with background, field-ionized H 2 0 in the tamed 0 0023 wt% boron, the same as that con-
APFIM tained in the "Mo-free type 316L" studied by
The amount of non-equilibrium segregation Karlsson and Nord6n [2] Overall, these alloys
increases with the increase in annealing tempera- were similar in composition and the grain bound-
ture and is strongly influenced by the cooling rate ary segregation behavior of boron and chromium
[11], with the largest amount of non-equihbrium was nearly identical
segregation occurring at some intermediate cool-
ing rate At an intermediate cooling rate, there is
sufficient time for vacancy-solute atom pairs to 5. Summary
diffuse to grain boundaries but not enough time
for the deposited solute atoms to diffuse away Grain boundary segregation of boron and its
from the boundary zone For non-equilibrium influence on the elemental distribution in the
segregation, the ability of a grain boundary to boundary region have been studied in type 304
serve as a vacancy sink is a dominant factor in stainless steel using a combination of aperture
determining the amount of segregation Experi- methods (TEM, FIM, AP) Grain boundary seg-
ments have shown that most gram boundaries, regation of boron, carbon, and phosphorus was
with the exception of special boundaries like twin found at all of the grain boundaries analyzed in
boundaries, can act as highly efficient vacancy the annealed type 304 Non-equilibrium segrega-
sinks [12] Therefore, the amount of non-equl- tion of boron was shown to be dominant with a
hbrlum segregation should be similar at the ma- maximum concentration at the boundary and a
jority of grain boundaries, whereas low-energy, tall of decreasing concentration away from the
G M Cannct/Apphed Surface Sctence 76 / 77 (1994) 266-271 271

boundary Segregation of carbon and phosphorus [3] T A Pruger, F Blake and J A Valley, Effects of Resid-
w a s c o n c e n t r a t e d at t h e g r a i n b o u n d a r y , i n d i c a t - ual Elements on Propertms of Austenmc Stainless Steels,
ASTM STP 418 (American Socmty for Testmg and Mate-
ing an equlhbrlum mode of segregation
rials, Phdadelphla, PA, 1967) p 23
C h r o m i u m w a s s h o w n to b e d e p l e t e d a d j a c e n t to [4] R Otterberg and W Roberts, Proc Stainless Steel '84,
t h e b o u n d a r y , b u t n o t to a n e x t e n t w h i c h w o u l d Goteborg, 1984, Book No 320 (Institute of Metals, Lon-
cause mtergranular corrosion fatlures, and don, 1985) p 229
r e a c h e d a m a x i m u m at t h e g r a i n b o u n d a r y [5] 1993 Annual Book of ASTM Standards, Vol 1 03, Sec-
tion 1, Iron and Steel Products (Amerman Socmty for
Testing and Materials, Phdadelphla, PA, 1993) p 42
[6] G M Carmcl, M G Hethermgton and G B Olson, J
6. Acknowledgements Phys (Paris) 49 (1988) C6-311
[7] D N Smloff, SS Brenner and M-J Hua, Mater Res
The author gratefully acknowledges Dr S S Soc Symp Proc 133 (1989)155
B r e n n e r for his i n c i t i n g discussions, a n d M r M -J [8] S S Brenner and M K Mdler, J Met 35 (1983) 54
Hua and Mr J Kowahk of the University of [9] J R Kearns, M J Johnson, G Aggen and W D Edsall,
Residual and Unspecified Elements m Steel, ASTM STP
P i t t s b u r g h for t h e i r a s s i s t a n c e m t h e e x p e r i m e n t s
1042, Eds A S Mehlh and E G Nlsbett (American Soci-
ety for Testing and Materials, Phdadelphla, PA, 1989) p
150
7. References [10] T M Wllhams, A M Stoneham and D R Haines, Met
Scl 10 (1976) 14
[1] H J Goldschmldt, J Am Iron Steel Inst 209 (1971) 900 [11] L Karlsson and H Norddn, Acta Metall 36 (1988) 35
[2] L Karlsson and H Nord6n, Acta Metall 36 (1988) 13 [12] R W Baluffi, Met Trans A 13 (1982) 2069

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