Effects of Composition on
Embrittlement of Austenitic Stainless Steels
A novel impact test is employed to evaluate the
of 14 elements with respect to embrittlement at 7500 F
ABSTRACT. Chill-cast austenitic
stainless steels are embrittled by
sigma and chi phase precipitation
during aging at elevated temper-
atures. The composition dependence
of this effect was studied using a
novel impact test of specimens aged
at 1500 F (816 C) for periods of time
up to 1000 hr. The effects of 15 ele-
ments were evaluated w i t h the aid of
multiple regression analysis. The
equivalent chromium content of an
alloy, w i t h respect to such embrittle-
ment, is related to its composition in
weight per cent by the following equa-
tion:
"Equiv. C r " = Cr + 0.31 M n
+ 1.76 M o + 0.97 W
+ 2.02 V + 1.58 Si
+ 2.44 Ti + 1.70 Cb
+ 1.22 Ta - 0 . 2 2 6 Ni
- 0 . 1 7 7 Co
Introduction
One of the considerations affecting
the choice of composition of stainless
steel castings and welding electrodes
for service at elevated temperatures
is their long-time structural stability.
If the service temperature is in the
range of 1 3 5 0 - 1 5 0 0 F ( 7 3 2 - 8 1 6 C),
the precipitation of sigma phase can
cause embrittlement w h i c h is m a n -
ifested in low values of the room-tem-
perature notched impact strength
after exposure. Since creep-rupture
strength and rupture ductility are in-
creased by the presence of sigma, 1 - 2
to the purpose of limiting sigma is to
protect equipment against fissuring
during repair weiding or cracking be-
cause of thermal shock or accidental
mechanical impacts w h e n the compo-
nents cool d o w n after a long period of
exposure in the embrittlement t e m -
perature range.
F. C. HULL is associated with the West-
inghouse Research Laboratories, Pitts-
burgh, Pa. Paper to be presented at the
AWS 54th Annual Meeting to be held at
Chicago, III.. April2-6, 1973
104-s I M A R C H 1973
chromium-equivalents
BY F. C. HULL
Sticka 3 investigated the effect of
aging on the impact properties of sev-
eral austenitic stainless steels to eval-
uate their structural stability for ser-
vice as power plant piping. Charpy
keyhole impact strength dropped on
aging to as low as 2 ft-lb. Sticka con-
cluded that lower "equivalent chro-
m i u m " contents would decrease the
susceptibility to embrittlement and
recommended that the chromium
equivalents of other elements be eval-
uated. Such information is supplied in
the present paper.
The current investigation was con-
centrated primarily on the class of Cr-
N i - M n - M o stainless steels, w i t h a
composition of 16% Cr, 2 0 % Ni, 1 0 %
M n , 2.25% Mo and balance iron,
referred to as Kromarc* stainless
steels. A n objective of this work was
to determine how much of various
alloying elements could be added to
this fully austenitic steel without
causing the steel to become suscep-
tible to embrittlement during long-
time service at elevated temperatures.
Experimental Procedure
Melting
Specimen preparation, designed
around the requirement that literally
hundreds of different alloys were to
be tested, was by levitation melting.
This technique had proven its value
as a convenient procedure for melting
alloys in a previous study of hot crack-
ing of stainless steels. 4 In the levita-
tion melting process, a 25 gram
charge, prepared by pressing the de-
sired amounts of pure r a w materials,
was levitated and induction-melted in
an argon atmosphere by means of a
specially shaped coil conducting high
frequency current. After a short induc-
tion stirring time, the current was de-
creased to permit controlled pouring
of the charge through an opening in
the bottom of the coil into a split
copper mold. The resulting casting
'Registered trademark of the Westing-
house Electric Corporation.
was in the form of a tapered pin ap-
proximately 2 in. long and 1 / 4 in. in
diam at the bottom end.
Materials and Composition
The raw materials used in the
preparation of the melts were electro-
lytic Fe, Cr, Ni, Cu and M n and high-
purity grades of Si, Co, Mo, W, V, Cb,
Ta, Ti, graphite, nitrided electrolytic
manganese, nickel-boron and sponge
zirconium. Except w h e n intentionally
added, the carbon content of the cast-
ings was 0.002-0.005% and the nitro-
gen content was about 0.0015%.
Phosphorus and sulphur were each
below 0.007%. The nominal composi-
tion of each sample was calculated
from the weights of the respective
elements charged.
In all, about 4 5 0 alloys were pre-
pared in three sets. For the 21 8 alloys
of Data Set I (Table 1) there were 22
series of alloys, in each series of
w h i c h a base or reference composi-
tion was selected, and then 10 to 15
samples were prepared w i t h a single
element varying in amount. For ex-
ample, Base A in Table 1 had a com-
position of 16% Cr, 2 0 % Ni, 3% Mo,
w i t h variable M n from 0 to 25% and
the balance Fe. The base composi-
tions and the ranges of the additions
were selected, w h e n possible, so that
the degree of embrittlement on aging
would vary from negligible to severe.
As seen from the nominal composi-
tions of the alloys in Table 1, Data Set
I included the following ranges of ele-
ments: 12-22% Cr, 5 - 5 0 % Ni, 0-35%
Co, 0-3% Si, 0-25% M n , 0 - 6 % Mo, 0-
6% W, 0-5% V, 0-5% Cb, 0-5% Ta, 0-
2.5% Ti, 0-5% Cu, 0-0.2% C and 0-
0.2% N.
There were 114 alloys in Data Set II
(Table 2) w i t h 19 heats of each base
composition. Combinations of W, V,
Ti and Cb w e r e studied in a factorial
experiment in Bases A and B: Mo, V,
Si and Ta in Bases C and D; and B, C,
N and Zr in Bases E and F. The re-
maining 118 alloys of Data Set III (not
tabulated) consisted of single, un-
related experimental alloys, commer-
cial stainless steels and less w e l l -
known steels described in patents.
Aging
Table 1 — Nominal Compositions in Weight Percent
The objective in this w o r k w a s to of the Series of Stainless Steels in Data Set I
evaluate the relative effects of differ-
ent elements on embrittlement due to Base Cr Ni Mn Mo Other
sigma or chi phase precipitation
during aging. A single aging temper- A 16 20 0 to 25 3
ature of 1 5 0 0 F (81 6 C) was employed B 16 20 10 to 25 1.5 0.1 Si
to provide a substantial response in a C 16 20 10 2 0 to 5 Cb
reasonable aging time. A g i n g at D 16 20 10 2 0 to 5 Ta
lower temperatures of 1000 to 1200 E 16 5 to 20 10 2
F ( 5 3 8 - 6 4 9 C) would have required F 16 7.5 to 35 10 3.5
G 16 7.5 to 50 10 5
excessively long aging times, and, at
H 16 40 10 5 0 to .2 C
temperatures above 1500 F (816 C), 0 to .2 N
1 16 40 10 5
the degree of embrittlement would J 16 5 to 40 10 5 10 Co
have decreased because of increased K 16 20 10 5 0 to 35 Co
solubility of the precipitating phases L 16 5 to 40 10 5 15 Co
in the austenite. A n advantage of the M 16 20 10 0 to 6
1500 F (816 C) temperature w a s that, N 16 20 10 2 0 to 6 W
at the low carbon level of many of the 0 16 20 10 2 0 to 5 V
alloys in this experiment, carbides did P 16 20 10 2 0 to 2.5 Ti
not usually precipitate on aging to an Q 12 to 22 20 10 3
R 15 to 26 20 10 0 0.1 Si
extent or in a form to complicate the
S 16 20 10 2 0 to 3 Si
interpretation of the results.
T 16 20 10 3.5 0 to .2 C
As w i l l be described in a later sec- U 16 20 10 3.5 0 to .2 N
tion, some compositions w e r e subject V 16 20 10 2 0.1 Si, 0-5 Cu
to catastrophic oxidation. W h e n oxi-
dation in air was so severe that it de-
stroyed the sample or interferred
w i t h the test, a replacement speci-
men was aged in an evacuated and
sealed tube (Fig. 1).
Table 2 — Nominal Compositions in Weight Percent of
the Series of Stainless Steel in Data Set II
Impact Test
ase Cr Ni Mn Mo Other
The impact test devised and used to
evaluate the degree of embrittlement A 20.5 15 7
is illustrated in Fig. 2. The procedure
consisted of subjecting a notched pin
held in a vise to successive 1.5 ft-lb B 17.5 12 15
blows from a freely falling hammer
until the pin fractured or was bent to C 21.4 12 2
a 9 0 deg angle. The specimen w a s
the as-cast pin in w h i c h a notch was
cut w i t h a hacksaw half-way through D 20.3 20 10
the pin.
In order to minimize the number of E 18 25 13 1.75 0.3
melts required for the present study,
each specimen was used to deter-
16 12.6 10 2.25 0.2
mine properties in all four conditions:
as-cast and after aging 17, 100, and
1000 hours at 1 5 0 0 F (81 6 C). There-
fore, the notch for the test of the as-
cast specimen was positioned near
the bottom of the pin, to conserve
tive nature, the technique was satis-
material, so that the same casting
factory for establishing the relation-
could be repeatedly aged, notched
ships desired.
and impact tested.
The number of hammer blows
Test Results
required to break a given specimen
varied from over 26 (for specimens Catastrophic Oxidation
that finally bent to a 9 0 deg angle E 3
without breaking) to less than one (for Some alloys that contained more
specimens so brittle that they broke than 4 % Mo, or more than 0.5% V in
w i t h less than a full swing). As this combination w i t h 2% Mo, exhibited
testing procedure provided only an i n - catastrophic oxidation during aging
exact measure of energy absorbed to for 1000 hr at 1500 F (816 C). This
fracture the specimen, it seemed type of attack, in its early stages, w a s
preferable to correlate the effects of localized in shallow pits. However,
composition w i t h the bend angle at
fracture, d, w h i c h could be measured
Fig. 1 — Effect of molybdenum and vana-
after the broken halves of the speci-
dium on the oxidation of Cr-Ni-Mn cast
men were placed back together. In stainless steels in air in 1000 hr at 1500 F 2 4 6
spite of its admittedly semi-quantita- (816 C) % Molybdenum

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1.5 ft lb Fig. 3 — Effect of aging at 1500 F (816 Cj

on the notched impact bend angle of 1/4
Maximum Capacity in. diam cast pins of steels containing 16%
Impact Tester Cr, 10-50% Ni, 10% Mn, 5% Mo, balance
Fe

Levitation Melted and Chill

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Fig 2 — Simple impact test to evaluate the embrittlement of cast stainless steel pins on %• 60 - \ \ -
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Measurements taken during the 20
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analysis of Data Set II provided an
in. diam specimens w e r e oxidized
estimate of the sources of variation of
completely. Usually compositions \ * _ g
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ponents of variation of the measure- % Chromium
also had a high sigma forming t e n -
ment for a given composition. The
dency, so that on both counts such
first is the " s p e c i m e n " variation be- Fig. 4 — Effect of aging at 1500 F (816 Cj
alloys would not be useful for high
t w e e n duplicate specimens of the
temperature applications. Sticka 3 on the notched impact bend angle of 1/4
same composition. The second is in. diam cast pins of steels containing 12-
observed catastrophic oxidation in
" f r a c t u r e " variation between t w o 22% Cr, 20% Ni. lOVoMn, 0.1% Si. 3% Mo.
his study of a Type 317 stainless
tests on the same pin for a given balance Fe
steel, w h i c h contained 3.5% Mo,
aging time, and the third is the " m e a -
during 4 6 , 0 0 0 hr aging at 1350 F
s u r e m e n t " variation between dupli-
(732 C) or 1450 F (788 C); but no
cate evaluations of the bend angle for
such attack occurred w i t h Type 316,
the same fracture. These individual
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and the total variances and standard
even in 6 1 , 0 0 0 hr at 1450 F (788 C).
errors of In $ are given in Table 3. V 8*\ \ \
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test results for 10 of the 22 series of variation about angles of 2, 10 and 50 £ 60

alloys in Data Set I are presented in deg. The $ + 2 o intervals include

Figs. 3-12. For Ni, Cr, M n , Mo, Cb, and approximately 9 5 % of the measure- \V vvioo \ \
Cu the bend angle, $ , is plotted versus ments. < 40
c
composition for the as-cast sample
and the three aging times. Note that
Microstructure
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the composition scale for nickel (Fig. The type of correlation that exists N. \n ^A
3) is reversed so that increased nickel between composition, microstructure
actually leads to less embrittlement. ^ ^ ^ ^ e ^
and bend angle is illustrated in Fig.
It w a s later found that the logarithm 3 5 10 15 20 25
13 A n alloy w i t h 16% Cr, 10% M n , % Manganese
of Q versus composition, as s h o w n in 5% Mo, 15% Ni and balance Fe
Figs. 9 to 12 for alloying additions of formed a large amount of precipitate Fig. 5 — Effect of aging at 1500 F (816 Cj
Ti, Si, W, and V, respectively, plotted in 1000 hr at 1 5 0 0 F (816 C) and failed on the notched impact bend angle of 1/4
as approximately straight lines, and w i t h a 2 deg bend angle. A s the nickel in. diam cast pins of steels containing 16%
this is the preferred representation. content was increased, the amount of Cr. 20% Ni, 0-25% Mn, 3% Mo, balance Fe

106-s I M A R C H 1973
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Fig. 6 — Effect of aging at 1500 F (816 Cj on the notched

bend angle of t /4 in. diam cast pins of steels containing
20% Ni, 10% Mn, 0-6% Mo, balance Fe
impact
16% Cr, V \ \
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Fig. 9 — Effect of aging at 1500 F (816 Cj on the notched impact
bend angle of 1/4 in. diam cast pins of steels containing 16%> Cr,
20% Ni, 10% Mn, 2% Mo, 0-2.5% Ti, balance Fe

100 1
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Fig. 7 — Effect of aging at 1500 F (816 Cj on the 60 •
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steels containing 16% Cr, 20% Ni, 10% Mn, 2% Mo, 0-
5% Cb, balance Fe - \ * 100 \
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Fig. 8 — Effect of aging at 1500 F (816 Cj ' Silicon
on the notched impact bend angle of 1/4
in. diam cast steel pins containing 16% Cr, Fig. 10— Effect of aging at 1500 F (816 Cj on the notched impact
20% Ni, 10% Mn, 2% Mo, 0 . 7 % Si, 0-5% bend angle of 1/4 in. diam cast pins of steels containing 16%o Cr,
Cu, balance Fe 20% Ni. 10% Mn, 2% Mo, 0-3% Si, balance Fe

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Fid. 11 — Effect of aging at 1500 F (816 Cj on the notched impact Fig, 12 — Effect of aging at 1500 F (816 Cj on the notched
bend angle of 1/4 in. diam cast pins of steels containing 16%> Cr, impact bend angle of 1/4 in. diam cast pins of stee/s con-
20% Ni, 10% Mn, 2% Mo, 0-6%, W, balance Fe taining 16% Cr. 20% Ni, 10% Mn, 2% Mo. 0-5% V, balance Fe

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Z7;^. 73 — Microstructure of chill-cast stainless steels containing 16% Cr, 10% Mn, 5%> Mo,
variable Ni and balance Fe after 1000 hr at 1500 F (816 C). X500. reduced 30%. (a) 15% Ni,
bend angle 2 deg; (bj 20% Ni, bend angle 4 deg; (cj 30% Ni, bend angle 20 deg; (dj 40% Ni,
bend angle 45 deg; (ej 45% Ni, bend angle 70 deg; (f) 50% Ni, bend angle 90 deg

108-s I M A R C H 1973
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Fig. 15 — Microstructure of chill-cast
stainless steel containing f6% Cr, 20% Ni,
10% Mn, 2% Mo and 2% W after WOO hr
at 1500 F (816 Cj. Bend angle 34 deg.
X500; reduced 49%

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F/ff. 74 — Microstructure of chill-cast stain/ess steels containing 16%> Cr, 10%, Mn, 5%,
Mo, variable Ni and Co, and balance Fe after 1000 hr at 1500 F (816 Cj. X500, reduced °', -° • %A A • " • .
41%. (a) 20% Ni, 10% Co, bend angle 7 deg; (b) 20% Ni, 20% Co, bend angle 45 deg; (cj ,J"" • ==» Q ' •' '<-„<!• • "
• . • > a *» JP- P . . :
35% Ni, 10% Co, bend angle 85 deg; (d) 20% Ni, 28% Co, bend angle 90 deg
Fig. 16 — Microstructure of chill-cast
stainless steel containing 16% Cr, 20% Ni,
10% Mn, 2% Mo, and 1% Ti after 1000 hr
at 1500 F (816 Cj. Bend angle 50 deg.
precipitate decreased and the bend 58 steel (Fig. 24). Some of these X500, reduced 59%
angle increased to over 9 0 deg. differences w i l l be explained by the
In the present study, cobalt was the electron micrographs described '
•**• '« tf. "% * * - . \ • - '-
only other alloying element, besides below and the phase identification p r
• •• y.x • ' -- -• o -
nickel, that decreased embrittlement. study. •J.'- ; ^ A \ ••• y "• .:,,
For three alloys w i t h a base composi-
tion of 16% Cr, 10% M n , 5% Mo, and Electron Micrographs
° O a .^. o , p- A . ° ,

2 0 % Ni, the cobalt contents w e r e 10,

20, and 28%. The amount of precip- Carbon extraction replicas w e r e ob- 5 •- P "•-- • . ' " " • • . - ' , .-• c .
itate as seen in Fig. 14 decreased tained on the 10 samples illustrated
w i t h increasing cobalt level and led to in Figs. 15-23. Electron micrographs ' v A - - .^.f \y - ^ A -:
an increased notched bend angle. A t of the replicas of these alloys w h i c h
a constant cobalt level of 10%, the had been aged 1 0 0 0 hr at 1500 F
amount of precipitate decreased as (81 6 C) revealed three different types
v ' y ,& »• • . ° .• . •
nickel w a s raised from 20 to 35%. of microstructures. Alloys w h i c h con- - ' • " • '
o?
- •
-
-
,
-
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In Figs. 15-18 microstructures are tained 3.5% M o or 2% M o plus W , Si,

F/ff. 7 7 — Microstructure of chill-cast
s h o w n after 1000 hr aging for alloys Ti or V had the appearance illustrated
stainless steel containing 16% Cr, 20% Ni,
w i t h a 16% Cr, 2 0 % Ni, 10% M n , 2 % in Fig. 25. Relative intensities of x-ray 10% Mn, 2% Mo and 1.5% Si after WOO
M o base and separate additions of diffraction patterns indicate that the hr at 1500 F (816 Cj. Bend angle 58 deg.
2% W, 1 % Ti, 1.5% Si or 1.5% V. large chunky particles in the alloy X500, reduced 48%
There are only minor differences in
the size and distribution of the precip-
itates in this group of alloys.
The effects of carbon and nitrogen
are s h o w n in Figs. 19-21 for an alloy
containing 16% Cr, 2 0 % Ni, 10% M n Table 3 — Estimates of Specimen, Fracture and Measurement Variance
and 3.5% Mo. Carbon (Fig. 20) Components and Total Variance With In $ Model Applied to Data Set II
seemed to increase the size and de-
crease the number of precipitates, Specimen Fracture Measurement Total
whereas nitrogen (Fig. 21) had the
opposite effect. However, neither Variance 0.222 0.0209 0.00087 0.252
carbon nor nitrogen significantly Standard Error 0.471 0.145 0.093 0.502
of In $
affected the bend angle after aging at
16= 2 0.8-5.1 1.5-2.7 1.7-2.4 0.7-5.5
1500 F (816 C).
0 1 2(7
Considerably different microstruc- 0 = 10 3.9-25.7 7.5-13.4 8.3-12.0 3.7-27
tures w e r e found in alloys to w h i c h Limits 1
tantalum or columbium had been \ 0 = 50 19-128 37-67 42-60 18-136
added (Figs. 22 and 23) or in Kromarc

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f/<7. 7S — Microstructure of chill-cast F/jgr. ?S — Microstructure of chill-cast F/ff. 2 0 — Microstructure of chill-cast
stainless steel containing 16% Cr, 20% Ni, stainless steel containing 16% Cr, 20% Ni, stainless steel containing 16% Cr, 20% Ni,
10% Mn. 2% Mo and 1.5% V after fOOO hr 10% Mn and 3.5% Mo after WOO Hr at 10% Mn, 3.5% Mo and 0.08% C after
at 1500 F (816 C). Bend angle 27 deg. 1500 F (816 C). Bend angle 19 deg. WOO Hr at 1500 F(816 Cj. Bend angle 40
X500, reduced 48% X500, reduced 48% deg. X5Q0, reduced 48%

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«y» . • * ' . " .
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y u « *• f -.,« * ; v .
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-; > " - • - » - ' ' A ' - • -"-" ^-;- •
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A"1 ~* *'. c 'r ' -% > ; • " » • • < • • ;.•• •„ • - ' _ ..."'..:'• i ' *
' - / v l :"'•,' ^' I •'•: «, * ;' -' V-' j-
^f--
'•>: >,-'• , ^ . .

.**.* "N * I ' -. y.~~

V

Fig. 21 — Microstructure of chill-cast

^\' A ' "
-'v ,-- •/•-•' m-:< ,;-;ii.>-*'\"t

Fig. 22 — Microstructure
A-. A\ ..
V- 1 'f A^A'^
of chill-cast
::">
- " •

f/ff. 2 3 — Microstructure of chill-cast

stainless steel containing 16% Cr, 20% Ni. stainless steel containing 16% Cr, 20% Ni, stainless steel containing 16% Cr, 20% Ni,
10%, Mn, 3.5% Mo and 0.12% N after 10% Mn. 2% Mo and 2.5% Ta after 1000 10% Mn, 2% Mo and 1% Cb after WOO Hr
WOO Hr at 1500 F (816 Cj. Bend angle Hr at 1500 F(816 Cj. Bend angle 48 deg. at 1500 F (816 Cj. Bend angle 59 deg.
24 deg. X500. reduced 48% X500, reduced 48% X500, reduced 46%,

containing tungsten are the chi phase a variety of smaller precipitate par- trides and MLC 6 , and t h e sigma and
and the lath shaped particles are the ticles. The largest particles in Fig. 2 6 chi phases are absent. After 1000 hr
sigma phase. are probably Fe 7 Ta 3 and t h e very aging at 1500 F (816 C), the Kromarc
As was indicated by the light micro- small particles are probably TaC. 58 specimen had a notched impact
graphs (Figs. 22 and 23), the electron In Kromarc 5 8 steel in the cast and bend angle of 53 deg. In a previous
micrographs confirm that the colum- aged condition (Fig. 27), t h e precip- study of precipitates in wrought Kro-
bium and tantalum additions produce itates are chromium and vanadium n i - marc alloys after creep testing, a
small amount of chi w a s found in
addition to the other phases. 5

Phase Identification

Table 4 — Effect of Alloying Additions on the Phases in Kromarc Type Stainless Precipitates for phase identification
Steels After Aging 1 0 0 0 hr at 1 5 0 0 F ( 8 1 6 C). Base Composition: were first obtained by extraction repli-
1 6 % Cr. 2 0 % N i , 1 0 % M n . 2 % M o . Balance Fe cas. Each powdered sample w a s
placed on a glass capillary and
mounted in a Debye Scherrer camera
Composition Phases Detected and Relative Intensities
for x-ray diffraction using Cr K a radi-
modification of Diffraction P a t t e r n s ' 3 '
ation. However, the amount of precip-
itate was too small to get satisfactory
3.5% Mo!! X — Mo B Cr 6 Fef 8 ,<r — C r M o M n "
(b) patterns in some cases. Other bulk
3.5% Mo + 0.08%C YS, o " m M „ C w
A. w
23 6 samples were then placed in a 1 0 %
2%W
1.5%'S s
ff .M23C^
Br-90% C H 3 0 H solution for about 16
3.5% Mo (h) + 0 . 1 2 % N o- hr. The solution w a s filtered by
1%Ti <J , T i C means of a Millipore filter to obtain a
1.5%V ff residue for x-ray diffraction. The mea-
1%Cb Laves — F e 7 C b J , Cr—Fe—Cb—Ni(Z Phase)" sured " d " values from the powder pat-
ffp , C b C w tern w e r e compared to " D " values re-
2.5% Ta Laves — F e j T a j , T a C ™ , M 2 3 C ^ , r j u w ported in the A S T M card file. The
p
Kromarc 58 Cr. N s , M 2 3 C * , V N phases present and the relative inten-
sities of the diffraction patterns are
(a) s = strong, m - medium, w = weak, vw - very weak, p = possibility listed in Table 4. Six of the ten alloys
(b) Total Mo
(c) Plus .15%N, .01%8, 01%Zr, .15%Si. 03%C, and 0.2%V
also contained F e 3 0 4 , w h i c h w a s

110-s I M A R C H 1 973
 - ' • • / - ' - ' . . -
present unless the alloy contained a
T A "*:"' deoxiding addition such as Si, Ti o r T a .
A "V- .VA'* 'A Although the tendency in the early
y:fy y^,y--' '..' j •' .." •

literature is to attribute the loss of

"•• r *'-AA ' A A ... "! /• "A . ' e*«. >/ impact strength on aging at 1350-
s ''' • , .." y * • . ~ \ 1550 F ( 7 3 2 - 8 1 6 C) solely to the pre-
/ ... :
. ' . • • • ' ' '. '•"•,
-/' '-'! cipitation of sigma phase, Table 4
. — — - - . ^ - . / • ' A„^ • indicates sigma and chi may both be
, ? .' "•,.•'
• '-{•
. . '.- • - ,
' • : ':,
.
' - /
\:-.\
'
' •' , \ \ > •
present in these C r - N i - M n - M o steels.
;
'.:• '.j. </.y:\ . • '••' / ' ;
AAA. Moreover, if columbium or tantalum

^~%,yyy:
_; 1 ,
are present, the principal source of
embrittlement may not be sigma, but
""'•'£• yy\
•s [
(
f
• *

some other intermetallic compound.

: ;
- . " \ ' • * • . • - • ' ' '• • ' / '

D i s c u s s i o n of R e s u l t s
f/ff. 24 — Microstructure of chill-cast
Kromarc 58 steel containing 16%, Cr, 20% Effect of Composition on Bend
Ni, 11.5% Mn, 2.2% Mo, 0.03% C, 0.13%, Fig. 25 — Electron micrograph of carbon Angle
N, 0.006% B, 0.009% Zr and 0.1%, Si after extraction replica of specimen with 2% W.
1000 Hr at 1500 F (816 Cj. Bend angle See Fig. 75. Chunky particles are chi and
In order to provide a means for eval-
53 deg. X500, reduced 46% laths are sigma. X4600, reduced 38%, uating chromium equivalents of ele-
ments, it was first necessary to estab-
lish a quantitative relationship
between embrittlement and total
alloy composition. A first order, linear
relationship between In e and the
total composition was assumed,
based on the previous observation
(Figs. 9-12) that the logarithm of the
bend angle varied linearly with
composition in a given base. Least
squares analyses were used to deter-
mine the coefficients in the resulting
empirical equations. The data for
zero, 1 7, 100 and 1 0 0 0 hr aging were
analyzed separately.
Table 5 lists the coefficients of the
terms in the equations relating In e to
composition, for alloys in Data Set I,
for each aging time, as w e l l as the
Fig. 26 — Electron micrograph of carbon Fig. 27 — Electron micrograph of carbon standard errors, F-ratios of terms and
extraction replica of specimen with 2.5%, extraction replica of Kromarc 58. See Fig. other measures of significance of the
Ta. See Fig. 22. Large particles are Fe7Ta3 24. Rounded particles in grain boundary regression analyses. For the 1000 hr
and very small precipitates are TaC. are /3Cr2 N and tiny particles are M23 C6 aging result, the following equation
X4600, reduced 38% and VAL . X4600, reduced 38%
illustrates the type of relationship
found between In e and the compo-
sition of the steel in weight percent.
CSJ
•
In e = 18.90 - 0.74 Cr - 0.24 M n
- 1.21 M o - 0 . 6 4 W - 1.28 V
o
o - 0.85 Si - 1.27 Ti - 0 . 7 2 Cb
"VI 5|*. ". .- „ - 0.43 Ta + 0.14 Ni + 0 . 1 2 Co
(D
Z 5 B ; " "" ' The ratio of the coefficient for a given
. "«" •,*•"/*; . " •
element to the coefficient for chro-
nz * — • , • » « * *
o * - j mium provides the chromium equiv-
CD
O
. Ai . . . alent of that element.
s
-' o " " • " Sigma or chi phase form in most of
o • " these chill cast samples on aging at
U_l^_ i " %
_J o 1500 F (816 C) and the amount of the
CD
-z.
cr phase and the degree of embrit-
a
. » •-•%,- "
o
2 o
UJ ° S 1 1 X WB »n
OO d ~
C3
D .
,-i Fig. 28 — Log-to of tne bend angle versus
a "Equivalent Chromium" for chill-cast
o
LT)
CD~
stainless steels aged WOO Hr at 1500 F
(816 Cj. Equation for "Equivalent
• • Chromium" is given on first page of this
O
article
O

fi 500 is! aoo 17j soo 20I000 22! soo 25J000 27!SOO 30! 000
EQUIVALENT CR

WELDING RESEARCH SUPPLEMENT! 111-s

 w i t h high columbium w e r e also differ-
ID (Nl
ent from other steels, in that, after an
OCN^tCOCMLOCNr^-OOCOCO
O c o c o o o r ^ . - r ^ c D L O . - . -
initial loss of ductility on aging 17 hr,
further aging increased the bend
angle(Fig. 7). This behavior may be re-
lated to the absence of appreciable
Lor^cMcNcNCOLOoocOT-r-^
r^LOCO^CNCMCNCOCNCNO
C N ' ^ O O C O C D T - C M C M ' — ^f (X
sigma or chi in this group of steels
and overaging of columbium interme-
tallic compounds.
CO LD
>-'-cx>,*^r^LOcNcT)rO'* In the first regression analyses,
•3-c\i.-cMCOLor^03^1-cooo
terms w e r e included for each alloying
^ • o o o o o o o o o o o
element in the steel. However, it
CO < N to LO m 0 0 in
01 t
O CN r- o turned out carbon and nitrogen were
co oo LO
r- CN
r^ ro co CN
CO
r~ —
.
CN CM CO CN 'JO CN r- >4
«- «-* not significant factors in determining
i t -
o
00
~
i i t- 1 I
«- i
embrittlement during aging at 1 500 F
(816 C). Boron up to 0.015% and zir-
conium up to 0.03% (amounts nor-
LO CO
O c n c O L o r ^ O c N - t f O O L O
mally used in alloys) also did not affect
Ocor^cDcOLOcNcocDcM^ embrittlement.
<- ' <- ' t-' •y CNi ^ ' i. r
Copper promotes the formation of
austenite and might have been ex-
c o L o O " * c N c o o o - - a ) > - o
cNcocNior-r--c>oOLOco
pected to be beneficial to impact prop-
•tf . - CO . - CO » - 00 >- LO r - erties. However, copper actually in-
creased embrittlement (Fig. 8), per-
00 00 haps by a precipitation reaction not
o LU r^'tfCDcNCOco'q-roco^-co o CM
related to sigma f o r m a t i o n , so that
o "d O N r - r 0 > t 4 C 3 O U ) ^ O O CD co
to C O O O O O O O ' - O O O O CO 03
the results for copper were not in-
W
*-< 0 cluded in the regression analyses.
c ro 03

<r
CN <* LO co LO < - 0 0 co <* CO
A standard procedure for testing
»9c ^ CN I O
r^ L O
oo CD
r-» CN
LO
CN CO CM
—c i
. —
. o
CD CO CN CJ) I O • " "
00
ti
c —
<D —
CU
o *-. the validity of an empirical formula,
ro O o such as In Q = f (composition), w h o s e
.2 <o coefficients were derived from one
3 «- CN LO
O " OO
Ol _ > OOcor-OLOcD'tf-'d-cDCO
OnOhMDhCDCNv-r-
set of data, is to calculate In 0 and the
5't r- CM V r ^ r i c j r - I standard error for a second set of
3 O
LL.
LU independent data, using the original
E§ o o equation. Notched impact tests,
0 T-
JZ c
o
LO ro cococococo^cDCDOOLoro w h i c h had been run on an unrelated
o ® cr group of 118 stainless steels from a
*~ u_
"D 0 A3
C O) k_
wide variety of categories (Data Set
«<
.C «j III), were used to make the compar-
r-> LU . - LO CO O CO , - LO CO CO CO o
S<2 COCO^-LOLOLOT-CNCOLOOtr r- ison summarized in Table 6. Although
58 m •q r ^ o o o o o ^ ^ o p o o .-
co a>
"2. * * -a
CD CO the standard errors of the predictions
a, are approximately twice as large for
Li- w
(ft < CNLOOOLOCOCOCO'-COOCOCO
LOcD>-OOr-coO'tcDr-~r^- Data Set III, the fit is reasonably good
« ja
^QJ O C O ' - O O C O C O r ^ i - O ^ t O O
considering that the ranges of c o m -
o .E
t (0
O
co r r r r r i' ^ >- r
o «- I I position for Cr, Ni and M n were con-
tJ w
. - CN
siderably different in Set III than in
CO ra >' O L O C M
O oo CD
CN r - co r^ co LO
| c o r ^ r ^ r ^ > - > — O
•* Set I, and that each alloy had a unique
1<3
ra " LU& composition rather than being one of
*- o
10 * •
- a group in w h i c h one element was
. c
w o O varied systematically.
ccu S CD O CO O co ^- CD LO o CD o
w QC ^t I- LO LO r- CD CN CN
t/i

1! Equivalent Chromium
LL
cc
0

< LU For the purposes of this paper, the

M- O •a CD 0 0 O "uj- CO 00 CM r - LO CN chromium equivalent of an element is
O *J LO CN « - LO ^ a i o i o ' t O ' -
tn < £ J
CO
r^ O O O O O f- o o o o defined as the % Cr that could be re-
a? _
(0 —
placed in an alloy by 1 % of the given
1 ^ element without altering the embrit-
.Ii
v> t i
CD
O
CO CO 5 f CM
CO CO CO LO
r-.«- o co
co LO r-- r- o r~- r-
co CN CN o »- r^ r^
CO CO CO LO CM CM O
tling tendencies on aging. Chromium
UJ
1
iS
• r i" i" r r o o equivalents from seven regression
1 CC • "n .2 P c
M-
runs w e r e averaged to obtain the
i n J2 s_ > O 0>
"O . M^ L. final expression:
2-S Ej i 5 5 ? > CO i
.a o
." «;
(U
oo "Equiv. Cr" = Cr + 0.31 M n
+ 1.76 M o + 0.97 W
+ 2.02 V + 1.58 Si
+ 2.44 Ti + 1.70 Cb
+ 1.22 Ta - 0 . 2 2 6 Ni
tlement increase as aging time in- sigma or chi but are caused by delta - 0.177 Co
creases. In the " a s - c a s t " condition, ferrite. The coefficients for the as- (2)
reduced bend angles at high contents cast alloy are thus measuring a differ-
of ferrite formers, such as Cr, V or Si, ent phenomenon than embrittlement The seven runs included equations in
or low nickel levels, are not related to during aging. The results on steels both f? and Inft results for 100 and

112-s I M A R C H 1 973

Table 6 — Standard Errors of In 0 W h e n the Equation Derived
With Data Set I Was Used to Predict for Data Set III
Data Set I
A g i n g Time No. of
at 1500 F (816 C) Observations
As Cast 72
17 hr 113
100 hr 178
1 0 0 0 hr 218
1000 hr aging tests, and equations
based on Data Sets I, III, (I + III) and (I +
II + III). Figure 28 is a plot of L o g l o 0
versus "equivalent c h r o m i u m " calcu-
lated by Eq. (2) for the 1 0 0 0 hr aging
results on 4 0 9 alloys from Data Sets
(I + II + III). The "equivalent chro-
m i u m " concept provides a convenient
means of combining on a single
graph, the effects of composition on
embrittlement during aging at 1 500 F
(81 6 C).
Summary
Stainless steels come in a wide
variety of compositions to fulfill many
different functions. The data present-
ed above show that embrittlement on
aging at 1500 F (816 C) is related to
the total alloy composition; some
compositions are essentially immune
to sigma and chi precipitation,
whereas in others it becomes a seri-
ous problem.
In practice one finds that as chro-
mium is increased to improve oxida-
tion or corrosion resistance; as
molybdenum is added to decrease
pitting attack; as molybdenum, t u n g -
sten or vanadium are added to in-
crease strength; as titanium, colum-
bium or tantalum are added to stabil-
ize carbon; or as nickel is decreased
to reduce cost or to provide delta fer-
rite in castings or weld deposits, the
tendency increases for embrittlement
to occur on aging.
The "equivalent chromium"
content of an alloy provides a semi-
quantitative relationship between e m -
brittlement tendencies and composi-
tion, such that the expected behavior
of an existing alloy can be estimated
or the composition of a proposed alloy
can be balanced in order to achieve a
desired result. For example, this rela-
tionship predicts that if the molybde-
num level of an alloy is increased by
1 % then chromium must be de-
creased by 1.76% or nickel increased
by 7.8% in order to maintain a certain
impact characteristic. The same sorts
of considerations apply to other
changes in composition.
Data Set III
Standard No. of Standard
Error Observations Error
.313 . 44 .60
.398 82 .84
.390 118 .92
.335 107 1.10
Whereas Sticka 3 indicated that
nickel did not influence sigma forma-
tion w i t h i n the composition range
covered by his group of alloys, the
present data show that nickel and
cobalt can have definite beneficial
effects. Their chromium equivalents,
however, are such that substantial
quantities of nickel or cobalt are re-
quired to offset the effects of such ele-
ments as Cr, Mo, W , V, Ti or Si. The
type of application, the service condi-
tions and economic factors must be
considered in determining how much
embrittlement can be tolerated and
the minimum level of nickel or cobalt
required to achieve this result. It
should be noted that manganese can-
not be substituted for all or a part of
the. nickel, from the standpoint of
embrittlement, since manganese pro-
motes sigma formation.
In the development of n e w stain-
less steels by the author, the aging
data were considered w h e n the c o m -
position of Kromarc 55 steel for high
temperature service was set at 16%
Cr, 2 0 % Ni, 10% M n , 2.25% Mo, and
balance Fe. The nickel is considerably
higher, w i t h respect to the chromium,
than in most commercial stainless
steels. For example, it is much higher
than it needs to be to prevent trans-
formation of austenite to martensite
on cooling to room temperature* or to
prevent the formation of delta ferrite
on solidification, because the nickel
content was determined by the
amount needed to minimize sigma
and chi precipitation.
These same considerations
entered into the design of a high
strength version of this class of alloys
called Kromarc 58 steel. 1 Although
molybdenum, tungsten, and vanadi-
um increase strength, since it had
been demonstrated that substantial
additions of these elements would
cause embrittlement, the desired
strength level was achieved instead
by small but effective additions of
*The stability of the austenite in these
alloys has led to their use for liquid hydro-
gen and helium bubble chambers.6
WELDING RESEARCH SUPPLEMENT!
vanadium, nitrogen, boron, and zir-
conium, w h i c h did not substantially
affect the impact behavior.
Conclusions
1. The embrittlement of highly
alloyed, chill-cast austenitic stainless
steels on aging at 1500 F (816 C) is
caused primarily by the precipitation
of sigma and chi phases, although
other phases were found in alloys
high in Cb o r T a .
2. Steels containing more than 4 %
Mo, or 2% M o and in excess of 0.5%
V, exhibited catastrophic oxidation
during 1000 hours exposure at 1500
F(816C).
3. The "equivalent chromium"
content of austenitic stainless steels
w i t h respect to embrittlement on
aging at 1500 F (816 C), is given by
the equation:
"Equiv. Cr" = Cr + 0.31 M n
+ 1.76 M o + 0.97 W
+ 2.02 V + 1.58 Si
+ 2.44 Ti + 1.70 Cb
+ 1.22 Ta - 0 . 2 2 6 Ni
- 0.177 Co
Acknowledgments
The writer gratefully acknowledges the
contribution of Mr. J. P. W e b b for the
preparation of samples, Dr. R. Stickler for
the electron micrographs, Mr. C. G. Beck
for the phase identification studies, Dr. K.
L. Kussmaul and Mr. R. Fardo for the
mathematical analyses and Dr. E. W.
Johnson for helpful discussions.
References
1. Hull, F. C , " A High Strength W e l d -
able Stainless Steel for Elevated Temper-
ature Service," Advances in the Technol-
ogy of Stainless Steels and Related Alloys,
STP No. 3 6 9 , A S T M , Philadelphia, 1 9 6 3 ,
pp 8 8 - 9 8 .
2. Garofalo, F., W h i t m o r e , R. W.,
Domis, F. W., and Von Gemminger, F.,
"Creep and Creep-Rupture Relationships
in Austenitic Stainless Steels," Trans.
American Society for Metals, 2 1 1 (4), pp.
310-319(1961).
3. Sticka, E. A., "Structural Stability of
Commercial W r o u g h t Austenitic Steels for
Power Plant Piping to 1 4 5 0 F," Proc,
American Power Conference, Vol. XXII,
IIT, Chicago, III. 1 960, pp 2 8 8 - 3 0 1 .
4. Hull, F. C , "Effects of Alloying A d d i -
tions on Hot Cracking of Austenitic Chro-
mium-Nickel Stainless Steels," Proc.
ASTM. Vol. 60, 1960, pp 6 6 7 - 6 9 0 .
5. Hull, F. C. and Stickler, R., "Effects of
Nitrogen, Boron, Zirconium, and Vana-
dium on the Microstructure, Tensile and
Creep-Rupture Properties of a C h r o m i u m -
Nickel-Manganese-Molybdenum Stain-
less S t e e l , " Proc, Joint International
Conference on Creep, Vol. 1, Paper 4 3 ,
August 2 5 - 2 9 , 1963.
6. Goodzeit, C , "Evaluation of Stainless
Steel Casting Alloys for 8 0 " Chamber
Body and Associated Parts," Brookhaven
National Laboratory Report E95: BC-01-
7G, July 1 9 6 1 .
113-s