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STRUCTURE,

CONSTITUTION, AND
GENERAL
CHARACTERISTICS OF
WROUGHT FERRITIC
STAINLESS STEELS
Sponsored by
Committee A-1 on
Steel, Stainless Steel, and Related Alloys

by J. J. Demo

ASTM SPECIAL TECHNICAL PUBLICATION 619

List price $7.50

04-619000-02

AMERICAN SOCIETY FOR TESTING AND MATERIALS

1916 Race Street, Philadelphia, Pa. 19103

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© by AMERICAN SOCIETY FOR TESTING AND MATERIALS 1977
Library of Congress Catalog Card Number: 76-42% 1

NOTE
The Society is not responsible, as a body,
for the statements and opinions
advanced in this publication.

Reprinted by permission from the

Handbook of Stainless Steels
edited by D. Peckner and 1. M. Bernstein
McGraw-Hill Book Company, New York

Printed in Baltimore, Md.

January 1977

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Foreword
This special technical publication appears as Chapter 6 of Handbook of
Stainless Steels published by McGraw-Hill Book Company and is reprinted
here by permission. Committee A-1 on Steel, Stainless Steel, and Related
Alloys of the American Society for Testing and Materials is the sponsor
of this publication.

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Related
ASTM Publications
Bearing Steels: The Rating of Nonmetallic Inclusion, STP 575 (1975),
$27.25 (04-575000-02)

Cleaning Stainless Steel, STP 538 (1973), $18.00 (04-538000-02)

Introduction to Today's Ultrahigh-Strength Structural Steels, STP 498

(1971), $3.75 (04-498000-02)

This publication is made possible by the authors and, also, the unher-
alded efforts of the reviewers. This body of technical experts whose dedica-
tion, sacrifice of time and effort, and collective wisdom in reviewing the
papers must be acknowledged. The quality level of ASTM publications is
a direct function of their respected opinions. On behalf of ASTM we
acknowledge with appreciation their contribution.

ASTM Committee on Publications

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Editorial Staff
Jane B. Wheeler, Managing Editor
Helen M. Hoersch, Associate Editor
Ellen J. McGlinchey, Assistant Editor
Kathleen P. Turner, Assistant Editor
Sheila G. Pulver, Editorial Assistant

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Contents
Structure and Constitution 2
Effect of Carbon and Nitrogen 3
Strengthening Mechanisms 5
Strengthening by Heat Treatments 6
Sigma Phase 7
475 °C Embrittlement 9
Summary 475 °C Embrittlement 19
High-Temperature Embrittlement and Loss of Corrosion 21
Background 22
High-Temperature Loss of Corrosion Resistance 23
High-Temperature Embrittlement 33
Notch Sensitivity in Annealed Alloys 44
Weldable, Corrosion-Resistant, Ductile Ferritic Stainless Steels 49
Low Interstitials 50
Interstitial StabiUzation 53
Weld DuctiUzing Additions 57
Sigma Phase and 475 °C Embrittlement Susceptibility 58
Molybdenum Additions 59
Summary 61

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J. J. Demo^

STRUCTURE, CONSTITUTION,
AND GENERAL CHARACTERISTICS
OF WROUGHT FERRITIC
STAINLESS STEELS

REFERENCE: Demo, J. J., Structure, Constitution, and General Characteristics of

Wrought Ferritic Stainless Steels, ASTM STP 619, American Society for Testing and
Materials, 1977.

ABSTRACT: High chroraium-ferritic stainless steels have good general corrosion and
pitting resistance and are resistant to stress-corrosion cracking. Despite these desirable
properties, the alloys have found little use as materials of construction. This lack of
use is a result of significant losses in ductility, toughness, and corrosion resistance
when these alloys are subjected to moderate or high temperatures. Names given to
the phenomena causing loss in properties include 475 °C, sigma phase, and high-
temperature embrittlement. This publication summarizes the literature describing the
causes, the cures, and the limitations imposed on alloys when these problems occur.
The most seriously limiting problem—high temperature embrittlement and loss or
corrosion resistance—is discussed in considerable detail. The key role that interstitial
carbon and nitrogen play on notch sensitivity and loss of ductility and corrosion
resistance following a high-temperature exposure as in welding is defined. Good as-
welded properties, the absence of which has severely restricted the use of ferritic
stainless steels, depend on controlling interstitial carbon and nitrogen. The publica-
tion describes three methods that are being used for interstitial control. It is now
possible to produce ferritic stainless steels which are tough and which have excellent
corrosion resistance and ductility in the as-welded conditions. Several new high-
chromium ferritic alloys with these desirable properties are being produced commer-
cially.

KEY WORDS: ferritic stainless steels, embrittlement, sigma phase, properties, corro-
sion resistance, notch sensitivity, interstitial, stabilization

The high chromium-iron steels represent the fourth class of alloys in the
family of stainless steels, the other three classes being austenitic, marten-
sitic, and precijjitation-hardening stainless and heat-resisting steels. Fer-
ritic stainless steels are iron-based alloys containing from about 12 to 16
'Senior consultant. Materials Engineering, Engineering Service Division, Engineering
Dept., E. I. du Pont de Nemours and Co., Inc., Wilmington, Del. 19898.

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STP619-EB/Jan. 1977

2 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

and 30 percent chromium. The high chromium hmit is arbitrary and is

meant simply to include all commercially produced alloys. Ferritic stain-
less steels, though known for more than 40 years, have had more restricted
utility and less wide use than the austenitic stainless steels. Reasons for
this include: the lack of the ductility characteristic of austenitic stainless
steels, their susceptibility to embrittlement, notch sensitivity, and poor
weldability, all factors contributing to poor fabricability. However, with
the increasing cost of nickel, the high resistance of the ferritic steels to
stress-corrosion cracking, and their excellent corrosion and oxidation
resistance, intensive research over the decade of 1960's has resulted in
ferritic alloy compositions which have good weldability and fabricability.

Structure and Constitution

In theory, the ferritic stainless steels are structurally simple. At room
temperature, they consist of chromium-iron alpha (a) solid solution having
a body-center-cubic crystal (bcc) structure. The alloys contain very little
dissolved carbon; the majority of the carbon present appears in the form
of more or less finely divided chromium carbide precipitates. They remain
essentially ferritic or bcc up to the melting point. A typical constitution
diagram, as published by the American Society for Metals UY is repro-
duced in Fig. 1. Attention is directed to the lower chromium end of the
phase diagram at the region of intermediate temperatures, about which
several points can be stated.
"C Atomic Percenfage Chromium "F
10 20 30 40 50 60 70 80 _ 90
2000 1 1 1 1 1 1 1 3600
'i "
mnn'
1800
L 1200

1600
Ci-L
i-^
2d
^ 21 -
-2800
I50S'
MOO'
1400
•a + ') / - 2400
ri
IZOO
LL
y -
- 2000
1000 ; 1
BZO' 1600
800 a+y. ^B50'
,V5\
770' ! 1 -
a-ta
600
Fe 10 20 30 40 50
A-,
60 70
i
80
!
90 Cr
1200

Weight Percentage Chromium

FIG. 1—Chromium-iron phase diagram (IJ.

^The italic numbers in brackets refer to tiie list of references appended to this paper.
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DEMO ON FERRITIC STAINLESS STEELS 3

1. Chromium is a member of a group of elements called ferrite formers

which extend the o-phase field and suppress the gamma (7)-phase field.
This property results in the so-called T loop extending in a temperature
range from 850 to 1400 °C.
2. As shown in Fig. 1, the transformation in chromium-free iron from
a to 7 phase occurs at about 910 °C. As chromium is added, the trans-
formation temperature is depressed to about 850 °C at 8 percent chromium
and then rapidly increased so that, at 12 to 13 percent chromium, the
transformation temperature is about 1000°C.
3. The transformation from 7 to a which occurs at about 1400°C for
pure iron is depressed with increasing chromium to about 1000°C at 12 to
13 percent chromium. At this point, the upper and lower temperature
curves for transformation join up to close off and form the 7 loop. Be-
yond 12 to 13 percent chromium, transformation to 7 is no longer possi-
ble, and an alloy would remain ferritic or bcc all the way from below
room temperature to the melting point. It will be seen that this maximum
limit for the existence of 7 phase is very much a function of austenitizing
elements and can be moved to higher chromium levels in the presence of
these elements, particularly the interstitials carbon and nitrogen. For al-
loys with less than about 12 percent chromium, an a -» 7 transformation
occurs on heating into the 7 range just as in pure iron. Ferritic stainless
steels cannot normally undergo this transformation upon heating and
cooUng.
4. Between the 7 loop and a-phase field, there is a narrow transition
region where an alloy at temperature will have both a and 7 phases which,
depending on the quench rate, may or may not be retained at room tem-
perature.

Effect of Carbon and Nitrogen

The location of the 7 loop in the iron-chromium phase diagram has
been carefully studied recently by Baerlecken, Fischer, and Lorenz [2].
These investigators used magnetic measurements at elevated temperatures
to determine the effect of carbon and nitrogen (and nickel) on the forma-
tion of austenite. The detailed a and 7 regions these workers developed
for pure iron and chromium alloys are shown in Fig. 2. The lowest point
in the 7 loop occurs at 840°C and 6.5 percent chromium. The greatest
width of the two-phase field is at about 1075 °C, and the complete en-
closure is reached at about 11.5 percent chromium. Since the greatest ex-
pansion of the 7 region is to about 10.6 percent chromium, the two-phase
7 + a region is very narrow in this high-purity alloy.
Additions of austenitizing elements, particularly carbon and nitrogen,
cause the outside boundary of the 7 -i- a two-phase field to shift to higher
chromium levels. The powerful effects of carbon and nitrogen in this

0 I * t e 10 n
% CHROMIUM
FIG. 2—Iron loop of the iron-chromium phase diagram for alloys with about 0.004 per-
cent carbon and 0.002 percent nitrogen [2].

regard are shown in Figs. 3a,b taken from work by Baerlecken et al [2],
Two effects are observed: namely, an expansion of the two-phase region
to higher chromium contents and the shifting of the maximum extension
of the 7 + a phase field to higher temperatures. For example, it is seen in
Fig. 3a that 0.013 percent carbon and 0.015 percent nitrogen shift the
maximum expansion of the 7 + a from 11.5 to 17.0 percent chromium,
while 0.04 percent carbon and 0.03 percent nitrogen shift it to about 21
percent chromium. At still higher carbon levels, for example, 0.2 percent.

% CHROMIUM

FIG. 3—Shifting of the boundary line C + «)/« '" tfte system iron-chromium through
increasing additions of carbon or nitrogen [2].

DEMO ON FERRITIG STAINLESS STEELS 5

an expansion to 26 percent chromium is observed. In addition, the point

of greatest expansion of the two-phase region is shifted to higher tempera-
tures, from about 1075 "C for the pure alloy to about 1300°C for an alloy
containing 0.2 percent carbon. The expansion of the two-phase region to
even higher temperatures is limited by the solidus temperatures of the
alloys. As evident from Fig. 36, nitrogen acts similar to carbon as a
powerful expander of the two-phase 7 + a field. In an alloy containing
0.25 percent nitrogen, the point of greatest width of the two-phase field
is shifted from 11.5 percent chromium for the pure alloy to 28 percent
chromium and to higher temperatures, from 1075 to about 1250 °C.
Besides its effect on extending the two-phase 7 + a region, carbon, be-
cause of its low solubility in the a matrix, is rejected from solid solution
as complex carbides, (Cr,Fe)7C3 and (Cr,Fe)23C6 which precipitate pre-
dominantly at the grain boundaries [3,4]- When an alloy is heated to tem-
peratures of 1100 to 1200°C and the carbon level exceeds about 0.01 per-
cent [2], the carbon cannot be held in solid solution even with rapid
quenching, and the complex carbides are formed, which drastically affect
the properties of the alloys.
It is at once obvious from this that whether or not an alloy remains
completely bcc depends very much on the chromium and the interstitial
levels. At low-chromium levels, even alloys with relatively low interstitial
levels may have a duplex structure when heated to temperatures around
1100°C. Alloys at the higher chromium levels can only have a duplex
structure if they also contain high interstitial levels; otherwise, these
alloys are fully ferritic at all temperatures. In general, beyond about a
13 percent chromium content, heating to high temperatures no longer pro-
duces massive transformation of a to 7; therefore, grain refinement and
hardening by heat treatment and quenching are no longer possible.

Strengthening Mechanisms
As just described, the ferritic stainless steels are characterized by the
essential absence of the a to 7 transition upon heating to high tempera-
tures. Consequently, hardening by the 7 to martensite transition upon
cooling will not normally occur. This transformation mechanism is
utilized in carbon and alloy steels and martensitic chromium-iron alloys
for achieving high hardness and strengths. The influence of heat treat-
ment temperature on hardness for two ferritic stainless steels and a
martensitic stainless steel are depicted in Fig. 4, based on data from Refs
5 and 6. In contrast to the 13 percent martensitic steel which undergoes
the a ^ 7 -»• martensite transition, the hardness on an 18 and 20 percent
chromium steel varies little with temperature. The fact that there is some
hardening occurring is due to the small amount of austenite formed at
temperature which is dependent upon the chromium content and inter-

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GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

27% c r i T y p c 4 4 e )

l a x c r cnrpE 430)

120 —

100 -
ISOO 1600 ITOO nOO 1900 2000 2100 2200 2300 2400
TEMPER4TUBE T

FIG. 4—Relative hardening of ferritic and martensitic chromium-iron alloys after water
quenching from indicated temperature [5,6].

stitial levels. For ferritic stainless steels, the hardening effect is strongest
at the lower chromium ranges but can occur even at higher chromium
levels if the carbon content is increased so as to expand the a to T, two-
phase region as shown in Figs. 3o,6.
In summary, it is not possible to harden or strengthen ferritic stain-
less steels significantly by heating them to high temperatures and cooling
rapidly. In these alloys, the slight increases in hardness or strength when
the alloys are heated above 850 °C are related to increases in grain size
(through grain growth) and the presence of small volumes of austenite
which reverts to martensite upon cooling.

Strengthening by Heat Treatment

Though a ferritic iron-chromium stainless steel cannot be strengthened
or hardened by the classical a ^ y -* martensite mechanism, the alloys
are susceptible to significant strengthening by heat treatment. In general,
the strengthening mechanisms that do occur are not desirable because the
alloys are embrittled, and ductility and toughness at room temperature
are severely reduced. Distinction will be made between three separate and
distinct forms of embrittling mechanisms: (a) sigma («r)-phase precipita-
tion, (ft) 475 °C embrittlement, and (c) high-temperature embrittlement.

DEMO ON FERRITIC STAINLESS STEELS 7

Surveys by Thielsch [6], Rajkay [7], Kaltenhauser [8], and Demo and
Bond [9] have summarized the extensive literature, describing these em-
brittling phenomena. These effects have been major deterrents to the use
of ferritic stainless steels as engineering materials. Because of their im-
portance to engineering properties, a summary of each of these em-
brittling effects is given here with details as to the nature and cure
of each.
Sigma Phase—This occurs in iron-chromium alloys containing between
15 to 20 and 70 percent chromium exposed to temperatures from about 500
to 800°C.
475 °C Embrittlement—This embrittlement occurs when a ferritic iron-
chromium stainless steel is heated between 400 and 540 °C. An increase in
hardness and tensile strength is observed, concurrent with a substantial
decrease in ductility and impact resistance.
High-Temperature Embrittlement—This embrittlement derives its name
from the fact that ferritic alloys with moderate to high carbon and nitro-
gen levels are brittle at room temperature following exposure of the
alloys to temperatures above about 1000°C.
While all these embrittling phenomena can affect severely the mechanical
properties of a ferritic chromium-iron stainless steel in an engineering ap-
plication, one is particularly serious, namely, high-temperature embrittle-
ment. This effect is serious because a useful engineering material must be
capable of being welded and heat treated while maintaining ductility, tough-
ness, and corrosion resistance.

Sigma Phase
Examination of the phase diagram in Fig. 1 shows a second zone at
lower temperatures centered about 45 percent chromium in addition to the
7 loop. A detailed part of the <r portion of the chromium-iron phase dia-
gram by Cook and Jones [10] is shown in Fig. 5. Pure c forms between
42 and 50 percent chromium, while a duplex structure of both a and c
phases has been found to form in alloys with as little as 20 and as much
as 70 percent chromium when they are exposed to temperatures between
500 and 800 °C. The existence of a compound in the iron-chromium sys-
tem at about 50 percent chromium was suggested as early as 1927 [11,12].
It was not until 1936 that the intermetallic compound, iron-chromium,
was definitely identified as <T phase [13,14]. <J phase is an intermetallic
compound containing one atom of iron with one atom of chromium
which is hard, nonmagnetic, and consists of a tetragonal unit cell. Ex-
tensive research has been reported describing the effort to establish the
structure and transformation characteristic of this iron-chromium com-
pound [15-20]. <^ phase forms in other alloy systems when two metals
with a bcc and face-centered-cubic (fee) structure are alloyed together

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8 GENERAL CHARACTERISTICS O F FERRITIC STAINLESS STEELS

Chranium. Weight %
iO 40 so 60 70
noo 1 i 1 1 •'" 1

• Single Phase cc '900

1600
• • Duplex atS
^ 1500 •
a • ^r
- 600
ee• • •
y* * a o e <t
•
liOO
'
•I - 1 TOO
a*d d a*S
1200 /
/ • ••
noo
e t a o » • o ,• - 600
SO SO 40 SO 60 70 60
Ciiromium, Atavic %

FIG. 5—Iron-chromium phase diagram in binary high-purity 25 la 76Cr alloys. This

diagram shows pure " phase from 44 to 50 percent chromium and mixed a and a phase from
about 25 to 44 and from 50 to 70 percent chromium with phase boundaries for temperature
interval of 1100 to 1500°F(595 to 8I5''C) [10].

and have atomic radii not differing by more than 8 percent [5]. Elements
like molybdenum, silicon, nickel, and manganese shift the <r-forming
range to lower chromium content [3,13,14,20,21]. a phase forms readily
on heating alloys containing 25 to 30 percent chromium to 600 °C but only
after a relatively long-time exposure. In alloys containing less than about
20 percent chromium, <T phase is difficult to form [5]. Cold work en-
hances the rate of <T-phase precipitation [14,19,21-24]. The formation
of a phase is accompanied by an increase in hardness and a severe re-
duction in ductility and toughness [25], especially when these properties
are measured at ambient temperatures. An important consideration is
that, in most chromium-iron alloys, (r forms very slowly, requiring
hundreds of hours. This is shown by the data in Fig. 6 from Short-
sleeve and Nicholson [20] describing the threshold times of (r formation
at 595 and 650°C as a function of chromium content. Based on these
data, weld deposits and casting normally would not have sufficient time
in the appropriate temperature ranges for a to form in alloys, especially
those containing 15 to 33 percent chromium [6\. Only with long iso-
thermal holds can a phase form to severely reduce the ductility and
toughness of chromium-iron alloys. A representative microstructure [25]
of a 27Cr alloy exposed for 3144 h at about 540 to 565 °C shows a
structure composed of ferrite, spheroidized carbides, and a phase (Fig. 7).
The <T phase has been precipitated as an essentially continuous series of
islands around the ferrite grain boundaries. Under some exposure condi-
tions, these islands are preferentially attacked (Fig. Id) indicating that the
presence of <r phase is also detrimental to the corrosion resistance of

DEMO ON FERRITIC STAINLESS STEELS 9

1 lOO • F (59S">C)
o Ferrite a Corbide
10.000 - • Ferrite a Carbide
a Sigma

I200°F(6S0»C)
\ \ ~ © Ferrite a Corbide
l/> ^ ® Ferrite a Carbide
a Sigma
I (000 o
V 4
\ \
i u.
e
i^
0
O
V\
o
o o V®

o
>s
tsj

o K
^
\
•
^V»
>.
too -' - §c o
T3
\ o^
3 C \9
O o
(D ax \
at
</)o
x:
a
®\

10 ——I ^ 1 1 '

15 20 25 30 35 40
Chromium %

FIG. 6—Effect of chromium content on the threshold times of a formation at 1100 and
nWFiSSS and650°C) [20].

chromium-iron alloys. Fortunately, <T phase developed in an alloy may be

brought into solution with relatively short holding periods of an hour or
more by heating at a temperature over 800 °C [6]. Alloys containing
nickel, molybdenum, and manganese may require longer holding periods
or higher temperatures to dissolve (T phase.

475 °C Embrittlement
When chromium-iron alloys containing 15 to 70 percent chromium are
subjected to prolonged heating at temperatures between 400 and 540°C,
the alloys harden, and a drastic loss in ductility is observed. The harden-
ing phenomenon is referred to as 475 °C (885 °F) embrittlement because
peak hardness on aging occurs at this temperature, as illustrated in Fig.
8 [6,25] for chromium-iron stainless steels heated for long times at
selected temperatures. The effect of prolonged heating at 475 °C on in-
creasing the strength and decreasing the ductility in an Fe-27Cr alloy is
shown in Fig. 9 from the work of Newell [25]. As suggested by these data,
hours of exposure at 475 °C are required before noticeable changes in
hardness and tensile properties are observed. However, notched speci-
mens may reveal this embrittlement in a much shorter time. Zapffe et al

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10 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

-^ S -5
.\

lilt
"111

800 "C.

0 SOD 400 600 800 1000 1200 MOO I600

Temperature. 'F

FIG. 8—Hardness surveys on bars after prolonged heating in a temperature gradient.

Analysis: 0.20 percent maximum carbon, 1.50 percent maximum manganese, 0.025 percent
maximum sulfur and phosphorus, 0.75 percent maximum silicon, 26 to 30 percent chromium,
1.00percent maximum nickel, 0.12 to 0.25 percent nitrogen [25].

120 •_ i
' 1 1 1 1 J
800 711^
TensHe Strength-, \^ • ;

-^ \
e 700- _ 100
N^
z -Yield Strength
1 '
40
oT
s
600 - &
§ 80 A1/
- ^' N
(-
z 500^
-
^
.^
Co
X\
a:
1-
) • \ I'
V\
U)
60
1 Elongation in 2 In.
1 L
1
40 1
300-

12 24 36 48 60 72 B4 96 108
Time, Hn
FIG. 9—Graph showing effect of aging time at 885 °F (475 °C) on room-temperature
tensile properties of27Cr-Fe alloy, air melted [25].

[24,26], using a 26Cr stainless steel, were able to show embrittlement on

notch specimens in a bend test after only the first half hour of exposure
at475°C.
Large reductions in impact strength may also be noticed after only
short-time exposure to embrittling temperature. Data taken from
Colombier's book [3] are summarized in the following table to illustrate
this point for a steel with 0.08 percent carbon, 0.4 percent silicon, and
16.9 percent chromium. The mechanical properties (tensile strength, yield
strength, and elongation) show essentially no effect of the embrittling
treatment, but a drastic loss in impact strength is recorded. As noted by

Annealed Heated 4 h at 450 °C

Tensile, tsi" 37.0 38.0
Yield point, tsi 21.0 25.4
Elongation, It 22.8 23.6
Impact values, kg/cm^ 12.0 1.4

"tsi = tons per square inch.

Colombier, after repeated heating in the range of 450 to 500°C, the

elongation starts to decrease and, after a few hundred hours, may be
virtually zero, while an increase in tension of some 7 to 8 tsi occurs.
The cause for the increase in strength and hardness and drastic re-
duction in ductility was unexplained for a long time. X-ray diffraction
analysis by Becket [27\, Riedrich and Loib [28], and Bandel and Tofaute
{29\ on specimens embrittled by heating in the neighborhood of 475 °C
showed no changes in lattice parameter. Newell [25], while reporting no
changes in lattice parameters, did note that an atomic disturbance was
occurring because the diffraction lines in back-reflection spectra of an
embrittled specimen were diffuse and broad. Early investigators could
detect no significant change in metallographic features, although Riedrich
and Loib [28] and Newell [25] did report a grain boundary widening.
Based on this observation, Riedrich and Loib concluded that the embrit-
tlement was caused by a precipitate along the grain boundary. In separate
work, Bandel and Tofaute [29] discovered that an embrittled 18Cr alloy
had a lamellar precipitate. Prior to 1951, 475 °C embrittlement was con-
sidered to be related to o^-phase formation and received the attention of
many studies. Newell [25] in 1946 showed that the embrittlement would
occur in practically carbon-free alloys as well as in those of moderate
carbon content. Bandel and Tofaute [29], Riedrich and Loib [28], and
Newell [5] showed that the degree of hardening as a function of tempera-
ture exposure was proportional to chromium content. The data from
Riedrich's and Loib's work using experimental low-carbon alloys are
produced in Table 1. The alloys in the annealed condition at the start
TABLE \—Hardnesses' of chromium-iron alloys after 1000 h exposure at 885 "F
(475°C) as a function of chromium content.

Chromium, % Brinell Chromium, % Brinell

by weight Hardness by weight Hardness

14.5 150 20.1 260

15.9 195 21.9 270
17.0 223 23.7 290
19.4 252 28.7 320

NOTE—Data by Newell [5] and Riedrich and Loib [28].

"The hardness of annealed alloys at the start was about 145 Brinell.

all measured about 145 Brinell. The hardnesses after 1000-h exposure at
475 °C are tabulated in the table. N. D. Newell's [5] data reproduced in
Fig. 10 also show the relationship of chromium content in commercial al-

110 i 1 I < ) 1 111

..
Temperature ees'R(W)"(;( 1^^
• r i l l III!
100 T^peifBfc^7%Cr)-.
r —
^4^ /
y

I 7jfpe4ip//7%trjL-^y'

,..i-—^
,,/• .Type-I/O Cie%Crj-
,> H--
T
10 =
^ ._
^Type 40S(iV'/cCr\Al)-Nonliar!ienabt
1 1 1 1 11111 1 1 1 1 1111
lO 100 lOOO
Time, Hours

FIG. 10—Age hardening tendencies at 885°F (475°C) of 12. 17, and27Cr-Fe alloys [S\.

loys to hardness increases. Rapid increases in hardness with exposure

times were noted for Types 446 and 430 stainless steel, with little change
noted for Types 410 and 405 stainless steel (12 percent chromium). These
data indicate that the hardening occurs in alloys containing over about
15 percent chromium, increases with chromium content, and is par-
ticularly pronounced for a commercial Type 446 stainless steel containing
26 percent chromium.
In 1951, Heger [30] emphasized the suggestion first made by Bandel
and Tofaute [29] and Newell [5] that the embrittlement was due to a
precipitation hardening process involved in the early stages of formation
of <r phase. This was in contrast to the theory of a minor impurity pre-
cipitation which was rendered untenable because alloy additions [30] and
prior heat treatment [29] did not improve resistance to the embrittlement,
and even the purest chromium-iron alloys embrittled [27], The cause, as
put forth by Heger [30] and Newell [5,25], was precipitation of some
phase which is inherent in the chromium-iron alloy system itself and not
an impurity. Heger postulated that 475 °C embrittlement occurred when a
chromium-iron alloy heated in the embrittling range undergoes the re-
action

a phase -• transition phase -• <r phase

The transitory phase that proceeds <r formation at higher temperature was
said to cause 475 °C embrittlement. Newell described the embrittlement
phenomenon as being related first to an initial lattice change or distortion

in the a matrix leading subsequently to gross precipitation of <^ phase

when the atomic mobility is increased at but slightly higher tempera-
tures. As Heger pointed up, the transition phase is intermediate in struc-
ture between a and <T and is coherent with the matrix a phase. The
presence of this coherency between the two different structures causes
large resistance to dislocation motion typical of a precipitation-hardening
mechanism [57]. The generated stresses then increase the hardness and
cause other property changes. While both Heger and Newell felt 475 °C
embrittlement was related to a transition state before a phase is formed,
Heger pointed up a very serious contradiction of this hypothesis.
Houdremont's [6,32] data reproduced in Fig. 11 illustrate this problem.
The alloys containing 17 and 28.4 percent chromium did not reveal any
hardening because of <r-phase formation (600 to 900°C). However, signifi-
cant hardening in the 475 °C embrittlement range (400 to 550 °C) did oc-
cur. It thus appeared that 475 °C embrittlement phenomenon is definitely
inherent to the chromium-iron binary system, as suggested by Heger and
Newell, but it is not related directly to the formation of T phase as
postulated.
Based on extensive research work from 1951 to 1964, two hypotheses
have been suggested to describe the mechanism of 475 °C embrittlement.
One school—Masumota, Saito, and Sugihara [33] and Pomey and Bas-
tien [34]—have attributed the changes in physical properties of alloys with
aging at about 475 °C to atomic ordering. In fact, Takeda and Nagai [35]
claimed to have found X-ray verification for super lattices corresponding
to FcaCr, FeCr, and FeCrs. However, all published attempts to observe
super lattices in chromium-iron a alloys using more sensitive neutron
diffraction have been unsuccessful [36-38]. The second and more preva-
lent school of thought for the occurrence of 475 °C embrittlement is the
formation of a coherent precipitate due to the presence of a miscibility
gap in the chromium-iron system below about 550 °C, in a chromium
range where a phase can form at higher temperatures. The data pub-
lished by Fisher, Dulis, and Carroll in 1953 [39] gave the first indication
of the presence of a coherent precipitate. These investigations were able
to extract fine particles about 200 A in diameter from a 28.5Cr alloy aged
for 1 to 3 years at 475 °C. The material was found to be nonmagnetic,
to have a bcc structure with a lattice parameter (a = 2.877 A) which is
between that of iron and chromium, and to contain chromium in the
range from 61 to 83 percent. Williams and Paxton [40] and Williams
[37] confirmed these results and were the first to propose explicitly the
existence of a miscibility gap below the tr-forming region in the equilib-
rium diagram of Fig. 1. The extent of the miscibility gap is shown in Fig.
12 as pubHshed by Williams [37]. Alloys aged within the gap would
separate into chromium-rich ferrite (a') and iron-rich ferrite (a). Rever-
sion to the unaged condition occurs when the specimens are heated above

TEMPERATURE — *F
eOO 80OJ0OO 1300 2000

sam SCO too mo ne 30B am not

TEMPERATURE — *C

TEMPERATURE — 'F
600 eOO 1000 LSOO ZOOO

JB7NV SOB 100 700 ao SCO 1000 mo

TEMPERATURE — 'C

FIG. W—Effects of temperature and aging time on hardness increase caused by 885°F
(475°C) brittleness and a-phaseprecipitation in several chromium-iron alloys [6,32].

1 1—1 1 ——r 1 1 1 1

— 1500
800 -

— / — 1400
\ Proposed by
\ v^'Williams

1300
700
~ n \ \
/ \ \
a
1 \ \ — 1200
1 \ \
1 /
600 --
\ \
i / / — 1100
a f fl . tf

/ 1 \

500 -
- K'""
_ /
\-f — _—_^ .
^
\
~
1000

- / \^ 900
/ • a \
/ 1
L 300

400 1 i — 1-., 1 1 I 1 1 1
0 0.1 0.2 0.3 0.4 0,5 0.6 0.7 0.8 0.9 1.0

ATOMIC FRACTION OF Cr

FIG. 12—Phase diagram of the iron-chromium system according to Williams [37].

550°C in agreement with all experimental data. The mechanism of age

hardening by «-«' precipitation in the chromium-iron alloy system has
been studied in detail by Marcinkowski, Fisher, and Szirmae [41] who
analyzed the influence of the formation of a chromium-rich precipitate
(a') on the deformation markings in the vicinity of hardness impressions.
In addition, using extraction-replica and thin-foil transmission electron
microscopy, these workers were able to show the existence of a coherent
chromium-rich precipitate in an iron-rich matrix in a 46 percent by weight
chromium-iron alloy heated for thousands of hours at 500°C (Fig. 13).
In more recent work on lower chromium content alloys, Grobner [42]
established the critical temperature range as well as the kinetics of the
embrittling process in chromium-iron alloys containing 14 and 18 percent
chromium. He showed that, for an 18Cr alloy, 475 °C embrittlement oc-
curs in a temperature range from 400 to 500 °C for both a commercial
purity alloy and a low interstitial alloy. However, the vacuum-melted
alloy of higher purity requires a longer exposure time to embrittle, as
shown by Grobner's data on impact strength reproduced in Fig. 14. In
addition to drastic changes in toughness, embrittled alloys, whether high

FIG. 13a—Electron micrograph of an extraction replica of bcc chromium-rich zones

existing in a 47.8 atomic percent chromium-iron alloy after annealing 9650 h at 500°C.

purity and vacuum melted or air melted, show increases in yield and
tensile strength and drastic reduction in elongation, as shown in Table 2.
Finally, Grobner showed that even steels with chromium contents as low
as 14 percent show embrittlement when exposed in the temperature range
of 370 to 485 °C, but only after much longer exposure times as compared
to the 18Cr steels.
Many investigators have studied the effect of additives on 475 °C em-
brittlement in chromium-iron steels [3,6,27,29,30,42]. Heger [30] noted
that, in general, the addition of alloying elements offered Httle or no
improvement in preventing the embrittlement. The effects of additives

FIG. 136—Transmission electron micrograph showing structure existing in a 47.8 atomic

percent chromium-iron alloy after annealing 3743 h at 500°C [41].

on 475 °C embrittlement taken from Heger [50] are summarized in Table

3. While not an additive, cold work [6] intensifies the rate of 475 °C em-
brittlement. In addition to drastic reduction in toughness and ductility,
embrittled chromium-iron alloys show a severe reduction in corrosion re-
sistance [24.29]. Data from Newell's article [24], tabulated in Table 4,
show that an embrittled alloy corrodes about four to twelve times more
rapidly in boiling 65 percent nitric acid than does an annealed specimen.
The accelerated corrosion on embrittled alloys is probably due to the
selective corrosion of the iron-rich ferrite formed because of the misci-
bility gap or, as suggested by Hodges [43], due to formation of chro-
mium-rich carbide precipitates.

I I I I lull I I I I mil I I I 1Mmil

ill II I I I I mil i i i i iii
: tlOOO

AIRMELTED

100

o
c

-J_ ••••' • ' • • • ••

I I I I m i | 1—I I I iiii[ 1—I I I iili| 1—I I I iiii| I—I I 11iw

•1000
VACUUM MELTED

2 100 —o—*- ooa

:->IOO

:-*IO

• ' '

FIG. 14—Impact strength at room temperature of half-size Charpy V-notch specimens

after aging at indicated times and temperatures; air-melted versus vacuum-melted 18Cr
alloys [42].

The 475 °C embrittlement may be alleviated and toughness and corro-

sion resistance restored by heating embrittled alloys at temperatures of
550°C and higher for a long enough time. As pointed up by Newell [24\,
1 h suffices to remove the embrittlement at 593 °C or higher, while 5
h are required at 582 °C, and over 1000 h at 538 °C. For compositions
susceptible to <^-phase precipitation in a relatively short time, as indicated
in Fig. 12, the 475 °C embrittled alloy can be heated to temperatures
above about 800°C (that is, above the (r-forming region) and rapidly
cooled to remove the embrittlement [6].

Summary 475 °C Embrittlement

Holding chromium-iron alloy in the temperature range of 400 to 540 °C
causes the alloys to become brittle and lose corrosion resistance. The

TABLE 2—Tensile properties at room temperature of a vacuum-melted and air-melted alloy

after indicated aging treatments.

Aged
- 0.2% Offset Tensile Elongation,
Alloy Temperat ure. Time, Yield Strength, Strength, % (50.8-mm
Type h ksi (MPa) ksi (MPa) gage)

1 0 30.9 (213) 49.9 (344) 32.5

1 316 4000 31.6 (217) 50.8 (350) 38.3
1 427 4800 69.8 (481) 84.1 (579) 13.0
1 482 2400 73.4 (505) 100.3 (690) 11.5
2 0 43.0 (296) 69.8 (481) 22.5
2 316 4000 38.5 (265) 69.1 (476) 25.5
2 427 960 73.7 (508) 95.8 (660) 17.0
2 482 2400 83.4 (540) 104.0 (717) 12.5

.'Mloy Cr C, % by weight N

1 vacuum melted 17.4 0.002 0.0031

2 air melted 18.0 0.044 0.09)1

NOTE—Data by Grobner [42].

TABLE 3—Effects of composition on 475''C embrittlement in

chromium-iron alloys.

Element Effect on 475 °C Embrittlement"

Cr intensifies
C no effect"; intensifies'
Ti, Cb intensifies
Mn lowers slightly
Si intensifies
Al intensifies
Ni low amounts; intensify
large amounts; decrease
N very slight"; intensifies'
P intensifies
Mo intensifies
Severe cold work intensifies'

"Heger [30].
'Grobner [42].
'Thielsch [6].

TABLE 4—Average rate of corrosion in boiling 65% nitric acid for

27Cr alloy after aging at 475 "C.

Condition Corrosion Rates, mil/year

Annealed 8.9
Embrittled 500 h at 475 °C 31
Embrittled 6000 h at 475 "C 109

NOTE—Data by Newell [25].

DEMO ON FERRITIC STAINLESS STEELS 21

embrittlement is caused by formation of coherent chromium-rich pre-

cipitate in the iron-rich matrix as a result of a miscibility gap in the
chromium-iron phase diagram below about 550 °C in the chromium range
from about 15 to 70 percent. The 475 °C embrittlement phenomenon and
ff-phase embrittlement are not related metallurgically. Significantly shorter
exposure times can cause 475 °C embrittlement, as compared to <T-phase
embrittlement. As with <T phase, it is unlikely that welding or a high-
temperature heat treatment can produce 475 "C embrittlement even if the
alloy experiences a relatively slow cool through the embrittling tempera-
ture ranges. A very heavy section may suffer 475 "C embrittlement
during cooling. The fact that 475 °C embrittlement or <T-phase embrittle-
ment will not normally occur in alloys welded or annealed at high
temperatures and then cooled makes these embrittling problems less
serious. However, alloys with more than about 16 percent chromium
should not be used for extended service between 370 and 540 °C, espe-
cially if the alloy is cycled from room temperature to the operating
temperature during process shutdowns or excursions.

High-Temperature Embrittlement and Loss of Corrosion

When high-chromium stainless steels of intermediate and high inter-
stitial content are heated above about 950 °C and cooled to room tempera-
ture, they may show a severe embrittlement [57] and loss of corrosion
resistance [44]. The effects can occur during welding, isothermal heat
treatments above 950°C, and casting operations. The effect on ductility
and corrosion resistance is shown in Fig. 15 [45] for a commercial AISI

'W1H.M1

FIG. 15—Effect of welding on (a) ductility and (b) corrosion resistance of AJSI Type
446 steel; 26 percent chromium, 0.095 percent carbon, 0.077 percent nitrogen; corrosion
tested in boiling ferric sulfaie-SO percent sulfuric acid solution [45].

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22 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

Type 446 stainless steel after it is welded. Of all the detrimental effects
which can occur in high-chromium ferritic stainless steels following
heat treatment, the so-called high-temperature embrittlement is most
damaging because operations such as welding, heat treatment, and cast-
ing—all operations necessary for a material of construction—can cause
serious loss in ductility and corrosion resistance. Not surprisingly, this
problem has been a severe deterrent, limiting extensive use of air-melted
ferritic stainless for commercial construction.

Background
Exceptionally thorough survey articles by Thielsch [6] and Rajkay [7]
summarize all the research done up to about 1966 on the causes for the
severe loss of corrdsion resistance and ductility when high-chromium
steels of moderate interstitial contents are heated to high temperatures.
Most early investigators studied either the embrittlement phenomenon or
the corrosion loss phenomenon, although, as latter investigators showed,
the property losses are related to a single mechanism. Up to the 1960's,
two theories were offered to explain the severe embrittlement.
1. The segregation or coherent state theory [6] postulated that em-
brittlement resulted from a clustering or segregation of carbon atoms in
the ferrite matrix. During rapid cooling, most of the dissolved carbon in
solid solution does not reprecipitate as carbides. Instead, the carbon
atoms in the supersaturated ferrite phase group as coherent clusters
which harden (that is, embrittle) the matrix, much in the manner of
certain age-hardening alloys. Annealing affected alloys between 700 and
800 °C causes the carbon to precipitate as carbides, thereby removing the
carbon atom clusters and the embrittlement.
2. In the martensitic mechanism first described by Pruger [46\, regions
in the alloy of relatively high-carbon content transform to austenite at
elevated temperature. During subsequent cooling, these regions transform
to brittle martensite. Annealing in a temperature range of 700 to 800 "C
removes the embrittlement by transforming the martensite to ferrite and
chromium carbides.
The theories proposed up to about 1960 to explain the severe inter-
granular attack on high-chromium ferritic alloys following high-tempera-
ture exposure are summarized next.
1. Houdremont and Tofaute [47] postulated that a carbon-rich
austenite forms at the sensitizing temperature. When cooled, easily dis-
solved iron carbides precipitate at the grain boundaries between the
austenite and ferrite phases. By annealing at about 750 °C, the iron
carbides are converted to chromium carbides which resist chemical
dissolution, and, therefore, the material becomes resistant to intergranular
attack.

2. Hochmann [44] also proposed the need for austenite formation at

temperature but suggested that intergranular corrosion occurs by
preferential attack on the grain boundary austenite phase itself because
of its low-chromium and high-carbon content.
3. Lula, Lena, and Kiefer [48] reject any mechanism of intergranular
attack that requires the formation of austenite. As they pointed up,
operations aimed at preventing austenite formation following high-
temperature exposure did not prevent intergranular corrosion. These
workers proposed that the stress surrounding the carbide or nitride pre-
cipitates formed during cooling are the cause of rapid corrosion on the
matrix adjacent to the precipitates. Annealing between 650 and 815 °C an-
nealed out the stresses caused by the precipitated phases, thus restoring
corrosion resistance.
An interesting point is the lack of any suggestion by the early in-
vestigators that the high-temperature loss in corrosion resistance was due
to chromium depletion adjacent to chromium-carbide precipitates. This
mechanism proposed by Bain et al [49] in 1933 and detailed by Ebling et
al [50] has been generally accepted as the cause of intergranular attack in
18Cr-8Ni austenitic stainless steels. Application of this phenomenon to
explain intergranular corrosion in a ferritic stainless steel was difficult be-
cause the effects of heat treatment on the austenitic and the ferritic
stainless steel were opposite. It was known that an austenitic stainless steel
would sensitize by holding in a temperature range from 400 to 800 °C and
that the corrosion resistance of a sensitized specimen could be restored by
heating to temperatures above about 950 °C which dissolved the chromium
carbide precipitates. In direct contrast, an air-melted ferritic stainless steel
is sensitized whenever it is heated above about 950 °C. Further, the corrosion
resistance of a sensitized ferritic specimen can be recovered by annealing in a
temperature range from 700 to 850 °C which corresponds to a part of the
range where an austenitic stainless steel is sensitized. In light of these con-
trasting effects, attribution of the chromium depletion theory as the mech-
anism for corrosion loss in ferritic stainless steel did not appear possible.

High-Temperature Loss of Corrosion Resistance

In the early and mid-1960's, a renewed interest in ferritic stainless
steels resulted in research studies into the mechanism for the high-temper-
ature embrittlement and corrosion loss phenomenon. It was Baumel in
1963 [51] who discussed the appUcation of the chromium depletion theory
to ferritic stainless steels. In the ten years between 1960 and 1969, in-
vestigations by Bond and Lizlovs [52], Bond [53], Baerlecken et al [2],
Demo [45,54], Hodge [43,55], and Streicher [56] confirmed that the
chromium depletion theory is the most plausible explanation for the
severe intergranular attack which occurs when alloys of moderate carbon

and nitrogen content are heated above about 950 °C and then cooled to
room temperature. Henthorne [57] has compiled an extensive summary on
the factors causing intergranular attack in iron- and nickel-base alloys.
Demo [54] showed, in 1968, curious effects of heat treatment on the
corrosion resistance of a commercial AISI Type 446 stainless steel exposed
to Streicher's ferric sulfate-sulfuric acid test (M. A. Streicher, ASTM
Bulletin, No. A229-58, April 1958, pp. 77-86, ASTM A262-70, Part 3,
and Ref 56). In a series of tests summarized in Table 5, he showed the
TABLE 5—Effects of thermal treatment on the corrosion resistance of AISI Type 446
stainless steel.'

Specimen' Corrosion Rate."

Designation Condition mil/year (exposure h)

1 as-received 30 (120)
2 30 min, 1100°C, water quench 780 (24)
3 30min, 1100°C, air cool 800 (24)
5 30 min, 1100°C, water quench + 30 min,
850 °C, water quench 42 (120)
4 30 min, 1100 "C, slow cool to:'
1000°C, water quench 767 (120)
900°C, water quench 27 (120)
800 °C, water quench 20 (120)
700 °C, water quench 18 (120)
600 °C, water quench 25 (120)

NOTE—Data by Demo [54].

"Exposed to boiling ferric sulfate-50% sulfuric acid solution (ASTM Recommended
Practice A 262-70, Part 3).
'See Fig. 6 for microstructure of designated specimens.
'2.5°C/min in furnace.

poor corrosion resistance of specimens water quenched or air cooled from

1100°C and the recovery when the sensitized specimens were reheated to
850°C. However, specimens which were cooled slowly in the furnace from
1100°C to temperatures below 1(XX)°C and then quenched displayed cor-
rosion resistance equivalent to the annealed specimen. Based on these data
and metallographic examination. Demo proposed two hypotheses but
favored the one describing the existence of a chromium carbide-nitride
precipitation range in the temperature region from 500 to 900 °C similar
to that observed for an austenitic stainless steel. Bond [53] in 1968 de-
scribed the effects of carbon and nitrogen level on the sensitization of
ferritic stainless steels containing 17 percent chromium. He concluded that
intergranular corrosion of ferritic stainless steel is caused by the depletion
of chromium in areas adjacent to where chromium-rich carbides and
nitrides precipitate. A portion of Bond's data is tabulated in Table 6 and
show the effects of interstitial levels on the intergranular corrosion re-

TABLE 6—Results of the boiling 65% nitric acid test on selected 17Cr alloys containing
carbon and nitrogen.

Corrosion Rate, mm/dm^ day, for the average of 5

Successive 48-h Periods After 1 h of Heat Treatment
at Indicated Temperature, water quench

1450°F 1700°F 1900°F 2100°F

Carbon, % Nitrogen, % (788°C) (926°C) (1038°C) (1150°C)

0.0021 0.0095 167 185 148 326

0.0025 0.022 164 944 761
0.0044 0.057 186 577 357
0.012 0.0089 126 824 1817
0.061 0.0071 147 619 1574

NOTE—Data by Bond [53].

sistance of a series of 17Cr alloys in boiling 65 percent nitric acid. Based

on these and other data, Bond concluded that a 17Cr-Fe alloy contain-
ing 0.(X)95 percent nitrogen and 0.(X)21 percent carbon was resistant to
intergranular corrosion after sensitizing heat treatment in the range of
9(X) to 1150°C. He also pointed up that alloys containing more than
0.022 percent nitrogen and more than 0.012 percent carbon were quite
susceptible to intergranular corrosion after sensitizing heat treatments at
temperatures higher than about 926 °C (]700°F). The low interstitial re-
quirement for resisting sensitization needs to be emphasized in contrast to
the interstitial levels of about 0.06 percent carbon and 0.03 percent
nitrogen in a typical air-melted 17Cr Type 430 stainless steel. Bond also
showed, through electromicroscopic examination of the alloys susceptible
to intergranular corrosion, grain boundary precipitates which were absent
in alloys not susceptible to such corrosion.
Demo [45] in 1971 showed that a 26Cr alloy containing 0.014 percent
carbon and 0.004 percent nitrogen after heating to 10(X)°C had excellent
intergranular corrosion resistance if quenched and poor resistance if air
(or more slowly) cooled. These results by Bond and Demo showed that
ferritic stainless steel could be subjected to high temperature without
resulting loss of corrosion resistance, providing low maximum interstitial
levels were maintained in the alloys, obviously much below levels for air-
melted alloys. For these low interstitial ferritic alloys, the response to
heat treatment is remarkably similar to that observed for austenitic
chromium-nickel stainless steels. If heated above 10(X)°C and water
quenched, the intergranular corrosion resistance is excellent, and no
grain boundary precipitates of chromium carbides are observed; upon
slow cooling, severe intergranular attack may be observed along with
grain boundary precipitates of chromium carbides [49,58]. A clear relation-

ship between heat treatment, the presence of an intergranular precipitate,

and corrosion resistance exists for a low interstitial ferritic alloy.
For a commercial air-melted Type 446 (26 percent chromium) stainless
steel. Demo [45] showed there is not a one-to-one correlation between
loss of corrosion resistance and the presence of a continuous grain
boundary precipitate in contrast to austenitic stainless steels and low
interstitial ferritic stainless steels. These results are shown in Fig. 16 for
specimens whose corrosion resistance is summarized in Table 5. For ex-
ample, specimens with microstructures numbered 2 (water quenched from
11(X)°C) and 3 (air cooled) had poor intergranular corrosion resistance
consistent with the continuous chromium-rich precipitates observed in the
grain boundaries. Specimens 1 (as-received) and 4 (cooled slowly from
1100°C) showed excellent intergranular corrosion resistance consistent
with the essential lack of any grain boundary precipitate. However, Speci-
men 5 (reheated at 850 °C) showed excellent intergranular corrosion re-
sistance but also a heavy grain boundary precipitate usually indicative of
poor corrosion resistance. It is lack of correlation between corrosion
resistance and grain boundary precipitate and the fact that commercial
alloys become sensitized when heated above about 1000°C that have held
back the acceptance of the theory that the high-temperature sensitiza-
tion problem in ferritic stainless steel is caused by chromium-rich pre-
cipitates formed at grain boundaries when the alloys are cooled through
a temperature from about 400 to 900 °C.
Using selected Fe-26Cr alloys of reduced interstitial levels. Demo [45]
defined the sensitization range for 26Cr-Fe alloys (0.1 in. thick). To do
this, he used alloys which had excellent corrosion resistance when
quenched from 1100°C but poor corrosion resistance if air cooled such
that the quenched alloys were supersaturated in carbon and nitrogen at
room temperature. The water-quenched alloys were then subjected to a
second heat treatment at selected times and temperatures between 400 and
10(X)°C. The alloys were corrosion tested and microstructurally examined.
From the corrosion data. Demo constructed a time-temperature-sensitiza-
tion envelope (TTS) for 26Cr-Fe ferritic stainless steel as shown in Fig.
17. The microstructure of selected examples (whose positions are marked
on Fig. 17) and their corrosion resistance are tabulated in Fig. 18. Speci-
men 1 heated at 1100°C and water quenched had good corrosion
resistance consistent with the absence of grain boundary precipitates.
Specimen 2, on the other hand, air cooled from 1100°C, had poor cor-
rosion resistance consistent with the grain boundary precipitates of
chromium-rich carbides and nitrides. Specimen 3, water quenched from
1100°C, then reheated at 900 "C, had good corrosion resistance and a
harmless discontinuous intergranular precipitate. Comparing micro-
graphs of Specimens 3 to 1 offers very strong evidence that chromium-
rich materials precipitate even at 900 °C, followed by agglomeration and
growth of the precipitates. Specimen 4, reheated for a short time at
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DEMO ON FERRITIC STAINLESS STEELS 27

700°C, exhibited good corrosion resistance, but the presence of a con-

tinuous intergranular precipitate is evident. At this temperature, the rapid
precipitation of chromium-rich carbides and nitrides to relieve super-
saturation was compensated for by almost simultaneous diffusion of
chromium which healed the initial chromium-depleted areas adjacent to
the precipitate. On the other hand. Specimen 5, heated for the same time
as Specimen 4 but at 600 °C, showed severe intergranular corrosion as
well as a continuous grain boundary precipitate. Under these conditions
of time and temperature, the rapid precipitation of chromium-rich pre-
cipitates occurred to relieve supersaturation; but, with reduced diffusion
rates, chromium atoms did not have time to diffuse into the depleted
areas. This fact is demonstrated by Specimen 6, also exposed at 600°C,
but for a long time (6 h). The specimen had a continuous grain boundary
precipitate, but, unlike Specimen 5, it had good corrosion resistance.
The longer hold time allowed the chromium atoms to diffuse into the
chromium-depleted areas adjacent to the grain boundary precipitate re-
storing the alloys corrosion resistance. In consideration of Fig. 17, the
line marking the low temperature side of the TTS band reflects the
minimum time and temperature required for chromium-rich carbides and
nitrides to precipitate from a supersaturated solid solution and to form
chromium-depleted zones. The line marking the high-temperature side of
the sensitization zone represents for 0.1-in. materi2il, minimum conditions
of time and temperature necessary for chromium diffusion to occur and
heal the depleted areas after the matrix supersaturation in interstitial
levels has been relieved by precipitation of chromium-rich carbides and
nitrides.
These data are consistent with the chromium depletion theory for inter-
granular corrosion. When ferritic stainless steels are heated above about
950 °C, the chromium-rich carbide and nitride precipitates are dissolved
in solid solution. If the interstitial levels are very low, they will be main-
tained in solid solution if the specimen is cooled rapidly. For these
quenched alloy compositions, the corrosion resistance is good. If these
alloys now supersaturated in carbon and nitrogen are subjected to
temperatures from about 500 to 950 °C, chromium-rich carbides and
nitrides precipitate rapidly to relieve supersaturation. In the tempera-
ture range of about 700 to 950 °C, almost as soon as precipitation oc-
curs, chromium diffuses into the chromium-depleted areas formed when
precipitation first occurred, increasing the chromium content of these
areas. Consequently, intergranular corrosion resistance is good, despite
the observed presence of an intergranular precipitate. In the tempera-
ture range of 500 to 700 °C where chromium-rich carbides and nitrides
rapidly precipitate, the resulting chromium-depleted zones are not healed
except during long hold times because the diffusion rate of chromium is
markedly lower at these lower temperatures.
In light of this description, the chromium depletion theory can also
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28 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

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900

800

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500

10 100
HOLD TIME AT TEMPERATURE (MINUTES)

FIG. 17—7TS diagram for Fe-26Cr alloys treated initially at IIOO°C, 30 min, water
quenched, then reheated at selected lower temperatures for different times; corrosion tested
in boiling ferric sulfate-50 percent sulfuric acid solution; (carbon + nitrogen) = 180 ppm
[45].

explain the effects of heat treatment on the corrosion resistance and

microstructure on the high interstitial alloys like AISI Types 430 and
446 stainless steel. For these alloys, in contrast to the low interstitial
alloys, even rapid quenching from temperatures above 950 °C is not fast
enough to prevent precipitation of chromium-rich carbides and nitrides
and chromium depletion results. This behavior is produced by the high
driving force for precipitation in the intermediate temperature ranges
caused by a combination of high interstitial supersaturation, rapid dif-
fusion of carbon and nitrogen as compared to chromium, and high
rates of precipitation in the ferritic matrix. The corrosion resistance of a
sensitized high interstitial alloy can also be restored by heating in the
temperature range of about 700 to 950 °C. This heat treatment permits
chromium to diffuse into the depleted areas, raising the chromium con-
tent and restoring corrosion resistance, even though a grain boundary
precipitate may still be observed in the microstructure (Specimen 5, Fig.
16). A long-time heat treatment in this temperature range, as used in com-
mercial annealing practices, may even allow sufficient time for the fine
grain boundary precipitate to agglomerate into large, discontinuous pre-
cipitates which are thermodynamically more stable and often observed
for long-time heat treatments (Specimens 1 and 4, Fig. 16).
In 1970, Hodges [43,55] demonstrated that high-purity alloys from
17 to 26 percent chromium were highly resistant to intergranular cor-

Cr
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rosion following exposures to temperatures above about 950 °C. Based

on his work, he concluded that sensitization in ferritic stainless steels
could be explained best on the basis of the chromium depletion theory.
Hodges noted that the sensitization-desensitization behavior of ferritic
stainless steels containing moderately low interstitial levels could be de-
scribed by the same type of TTS curve as reported for austenitic stain-
less steels, the difference being that the time sequence for sensitization-
desensitization for austenitic stainless steel is minutes and hours, but only
seconds and minutes for ferritic stainless steels. Hodges also showed
that molybdenum as an alloying element in high-purity ferritic stainless
steels shifts the sensitizing envelope to longer times, thereby delaying
sensitization and loss of intergranular corrosion resistance. Streicher
[59] showed that, for high-purity ferritic alloys, the interstitial levels
which are tolerable without sensitization occurring is increased when
molybdenum additions up to 6 and preferably 4 percent are made.
Streicher [56] has studied in detail the effects of carbon and nitrogen
level and heat treatment on the microstructure and corrosion resistance
of chromium-iron alloys. In particular, he has documented carefully the
regions of attack in specimens which are fully ferritic or a mixture of
ferrite and austenite, depending on where the alloy composition was lo-
cated according to the phase diagrams in Fig. 3 when it was exposed to
high temperatures. As an example taken from his work, a commercial
Type 446 steel (26 percent chromium) containing 0.098 percent carbon and
0.21 percent nitrogen contains up to about 40 percent austenite when
water quenched from a heat treatment at 1150°C. As shown in Fig. 19a
from Streicher's work, no chromium-rich precipitates of carbon and
nitrogen are formed at the boundary between austenite grains or in the
austenite grains themselves because of the high solubility of carbon and
nitrogen in austenite. When this specimen was subjected to the ferric
sulfate-sulfuric acid corrosion test, (Fig. 196), severe intergranular attack
occurred at the ferrite-ferrite and ferrite-austenite boundaries because
carbon and nitrogen were rejected due to the low interstitial solubility in
ferrite. However, no attack is observed at the austenite-austenite
boundaries because the interstitials are maintained in solid solution due
to their high solubility in austenite. Streicher [56] also showed that
heat treatments have no detrimental effects on the intergranular corrosion
susceptibility of high-purity 16 and 25Cr-Fe stainless steels (carbon <
0.0086 percent, nitrogen < 0.0025 percent). From his work, he also
concludes that the chromium depletion theory can adequately explain
intergranular corrosion and other forms of localized attack occurring in
chromium-iron stainless steels.
Based on the work of a number of investigators, the high-tempera-
ture loss of corrosion resistance observed when ferritic alloys of high
interstitial contents are heated above about 950 °C may be explained by

-7' .--/^"

J :-xV.-^--

• . . - - ^ • ' ^ - - y - N •-.••

FIG. \9a—Structure of Type 446 steel heated at 1150°C (x500). Etched surface shows
"dot" precipitate in ferric matrix, but not near austenite grains, which have absorbed
carbon and nitrogen from adjacent ferrite.

the chromium depletion theory which is accepted widely as the cause for
sensitization in austenitic stainless steels. No support for alternate theories
proposed to explain the high-temperature corrosion loss phenomenon can
be found. These alternate theories were based on (a) preferential dis-
solution of iron carbides, (b) accelerated corrosion due to stresses sur-
rounding chromium rich precipitates, (c) presence of austenite or its de-
composition products at grain boundaries, and (d) galvanic action be-
tween the precipitate and the surrounding metal matrix.

High-Temperature Embrittlement
Whenever commercial high chromium-iron ferritic stainless steels con-
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Downloaded/printed by
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34 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

FIG. \9b~Initial attack of ferric sulfate solution on Type 446 steel heated at 11S0°C.
water quenched (x500). Intergranular attack on ferrite-ferrite and ferrite-austentite boun-
daries. No intergranular attack on austenite-austenite boundaries. Localized attack on dot
precipitates which are absent in zones near austenite grains but not at ferrite-ferrite boun-
daries; exposed J 4 h in boiling ferric sulfate-SO percent sulfuric acid solution [56].

taining moderate to high interstitial levels are heated above about 1000°C,
the alloys at room temperature show an extreme loss in toughness and
ductility. If an embrittled alloy is reheated in a temperature range of
750 to 850°C, the ductility of the alloy is restored. Two early theories,
coherent state and the martensitic mechanism, proposed to explain this
high-temperature embrittling phenomenon were described earlier. Baerlacken
et al [2], Demo [45], Semchyshen et al [60], and Plumtree et al [6]] have
shown through their work that high-temperature embrittlement is related to
interstitial levels in the alloy just as is loss of intergranular corrosion resis-
tance.

Baerlecken et al [2] studied the effects of heat treatment on the tough-

ness (impact strength) of air-melted steels containing moderate levels of
carbon and nitrogen and vacuum-melted steel containing very low inter-
stitial levels. Using air-melted steel, these workers concluded that the
variable toughness as a function of heat treatment and chromium con-
tent was connected with the structure and morphology of the carbide
precipitates. Using high-purity, vacuum-melted alloys given a two-stage
heat treatment (30 min at 1050 °C cooled to 800 °C for 25 h) these
workers showed that the impact transition temperature was shifted to
higher temperatures as the chromium content increased. However, if these
same low interstitial alloys were given a second high-temperature heat
treatment by reheating to 1050 °C which would normally embrittle a high
interstitial alloy, they discovered that excellent low-temperature impact
values were observed for alloys at all chromium levels. These results are
shown in Fig. 20 from their work. They explained this effect of heat
treatment on toughness by the fact that the solubility of the interstitials
in the a solid solution decreases with increasing chromium content. There-

CHROMIUM: 16%

o 30 MIN. 1050 °C/OVEN

25h 80O«C/AIRC00L
• 30 MIN. 1050 'C/OVEN
25h 800«C/AIRC00L
• 30 MIN. I050°C/WATER

» 100 ?

-SO -to-20 0 10 10 so 80 wo m no leo m zoo

TESTING TREATMENT IN 'C

FIG. '20—Effect of heat treatment on position of the sharp drop of the notch impact
toughness-temperature curve of vacuum-melted chromium steels with 16 to 30 percent
chromium [2].

fore, the initial two-stage heat treatment on specimens of the same inter-
stitial levels produces more precipitates of carbides and nitrides the higher
the chromium content of the alloy is, with resulting decrease in tough-
ness (that is, increase in the transition temperature). On the other hand,
by a second solution heat treatment and rapid quenching, it is possible
even with steels of high-chromium content (and reduced carbon and nitro-
gen solubility) to keep the very low interstitial levels of vacuum-melted
alloys in solid solution. Therefore, carbides and nitrides do not precip-
itate, and their deleterious effects on notch impact toughness do not oc-
cur. Another important conclusion from their work is that grain size has
little effect on notch impact behavior because high-chromium, vacuum-
melted alloys even with grain size ASTM 1-3 displayed transformation
temperature of about -40°C.
Demo [45] studied the effect of thermal treatment on the ductility of
high and low interstitial purity alloys containing 26 percent chromium. As
shown in Table 7, loss of ductility is observed only when the commercial
TABLE 7—Effect of thermal treatments on the ductility of stainless alloys.

Elongation (in 25.4 mm) for the Indicated

Stainless Steels After Heat Treatment

AISI High Purity AISI

Condition Type 446 26Cr Type 304

Annealed 25 30 78
30 min, 1100°C, water quench 2 30 84
30min, 1I00°C, air cool 27 32 85
30 min, llOO'C, slow cool' to 850 °C,
water quench 33 30
30 min, 1100°C, water quench + 30
min, 850 °C, water quench 27 29
120 min, 677 °C, air cool- 84

NOTE—Data by Demo [45].

'•0.014% carbon, 0.004% nitrogen.
'Cooled in furnace at 2.5°C/min.
'A heat treatment known to cause sensitization in AISI Type 304.

AISI Type 446 stainless steel containing high interstitial levels is heated to
1100°C and water quenched. Importantly, the same alloy cooled more
slowly from the high-temperature exposure (that is, air or slow cooled)
shows excellent ductility, as does the embrittled alloy when it is annealed
by a second heat treatment at 850 °C. In contrast, the ductility of the low
interstitial 26 percent chromium steel is not adversely affected by heat
treatment. These observations suggested to Demo that loss of ductility
(that is, tensile elongation) in chromium-iron alloys when heated to high
temperature, as in welding or isothermal heat treatment, was also related

to interstitial content, as suggested by Baerlacken et al, and cooling rate.

Demo also examined the fractured edges of the heat-treated, air-melted
Type 446 stainless steels in cross section, as shown in Fig. 21. The water-
quenched specimen (brittle) shows intragranular cleavage. The air-cooled
specimen (ductile) shows intergranular cleavage with some localized de-
formation and elongation of the grains. The slowly cooled specimen
(ductile) shows a fibrous shear structure with considerable localized de-
formation and elongation of the grains. Based on these observations.
Demo concluded that precipitation of carbides and nitrides in the grain
boundaries does not grossly affect ductility because both air-cooled and
water-quenched specimens had intergranular precipitates, but the failure
mode in the brittle specimen was predominantly intragranular. Moreover,
an embrittled specimen reheated to 850 °C shows restored ductility de-
spite the presence of a heavy intergranular precipitate, as shown in Fig. 16
(Specimen 5). Finally, as shown in Table 7, an 18Cr-8Ni austenitic stainless
steel, which has been sensitized by heating at 677 °C to cause grain boundary
precipitation of chromium carbides, retains excellent ductility.
Using thin-film electron microscopy examination, Demo has shown
structural difference between embrittled and ductile alloys. Transmission
micrographs of the water-quenched specimen (brittle) and the air-cooled
specimen (ductile) are shown in Fig. 22. For the water-quenched speci-
mens, precipitates are noted, not only in the grain boundaries as expected
from the optical micrographs, but also on nearly all dislocations. On the
other hand, no precipitates are observed on the dislocations of the air-
cooled specimens, although grain boundary precipitation is shown in the
optical micrograph. Unrestrained motion of the dislocations in the water-
quenched specimen is blocked by the precipitate, with a resulting increase
in strength and reduction in ductility and toughness.
Demo proposed that precipitation of chromium-rich carbides and nitrides
on dislocations in the grain body and not on grain boundary surfaces is
responsible for the severe loss in ductility when ferritic alloys are heated
to high temperature. Demo suggests two possibilities to explain why chro-
mium-rich precipitates form on dislocations in rapidly cooled specimens
and not on more slowly cooled specimens, even though both contain
chromium-rich precipitates in the grain boundaries. First, the high inter-
stitial contents of the air-melted alloys, combined with the high interstitial
supersaturation, serves as a strong driving force during quenching for rapid
precipitation on all high-energy surfaces such as grain boundaries and
dislocations. During a slower cool, the longer relative time available to
relieve supersaturation may allow for diffusion of carbon and nitrogen
to grain boundary areas where the supersaturation is relieved by precipita-
tion on the more preferred higher energy surfaces of the grain boundary.
An alternate explanation is that dislocation nucleation during the rapid
quench occurs simultaneously with rejection of carbon and nitrogen as
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38 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

L^*< ^
a ^
^ > •1
-I . ti
0) o )o
• eO 5
o
0
o CO ^
1
o g §
-Q • ^

z Hi
s o '5>
S8 |3! ^•*
5—
c
c "2:
Si S
5 ^
0 ^
l^
*<?i
c S
•2--.

d 1^
a V.
<
o
^1
<y >n

i-".'_-^.£i.'. i 0
O
g—r
l]fl
o a^
z ^s^
S "^1
|-5
'i-'::-.- - '.'" '•: O ^«
y- - , - •^
to
II
d |«
3: e
o"
0
O
1*
S '<^

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• ' t-' •' ^'- -''
z
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fl
S ^i
i|

i 11*.
(a) Water quenched.
FIG. 22—Transmission electron micrographs of an AISI Type 446 stainless steel heated to
1100°C; 0.095percent carbon, 0.077percent nitrogen [54].

*^p''

9 ' . • • ' ^

(b) Air cooled.

FIG. 21—Continued.

chromium-rich carbides and nitrides precipitate to relieve the supersatura-

tion. With a slower cool and, therefore, reduced thermal stresses, relief of
supersaturation by precipitation on high-energy surfaces may occur before
dislocations are nucleated by the effects of thermal stresses. Demo asso-
ciates the poor ductility of chromium-iron alloys subjected to high-tem-
perature exposure to fine, dispersed precipitates in the matrix preventing
easy movement of dislocation similar to a hardening mechanism in a pre-
cipitation-hardened alloy [62], An increase in strength is observed with a
concomitant tremendous reduction in ductility and toughness.
Semchyshen, Bond, and Dundas [60] have reported the effects of chro-
mium, carbon, and nitrogen levels and heat treatment on the toughness
(impact resistance) of chromium-iron alloys containing from about 14 to
28 percent chromium. The impact resistance of a 17Cr steel in the annealed
condition as a function of carbon content is shown in Fig. 23a. Note the
relatively low transition temperatures even at carbon levels of 0.061 per-
cent. These data may be contrasted with impact energy absorbed for the
same specimens sensitized by heating to 1150°C as shown in Fig. 23b.
When the carbon content of the alloys exceeds about 0.018 percent car-
bon, a large increase in transition temperature is observed. As noted,
these alloys contain low levels of nitrogen (<0.0010 percent). These same
workers repeated this work on a series of alloys containing increasing
levels of nitrogen, with carbon being held to low levels below 0.004 per-
cent. The impact data for the annealed specimens and those annealed, as
well as heated at 1150°C are shown respectively in Figs. 24a,b. The an-
nealed specimens containing nitrogen up to 0.057 percent displayed excel-
lent impact resistance. However, when the nitrogen content in the 17Cr
alloys exceeded about 0.022 percent nitrogen, the impact transition tem-
perature was shifted to high temperatures following a thermal treatment
at 1150°C. The same effects between carbon, nitrogen, heat treatment,
and impact resistance were found for alloys containing 26 percent chro-
mium. Semchyshen et al also showed that a 17Cr alloy containing 0.01
percent carbon or 0.02 percent nitrogen contained grain-boundary precipi-
tates, while alloys of higher purity remained free of grain boundary pre-
cipitate after quenching from temperatures above about 925 °C. Based on
these data and observations, they conclude that high-temperature embrit-
tlement (that is, the observed increase in transition temperature when
ferritic alloys are quenched from temperatures above about 1000 °C) is caused
by precipitates of chromium-rich carbonitrides mainly on the grain boundaries.
Plumtree et al [57] showed in recent work that the impact transition
temperature increased linearly with the total interstitial content for 25Cr-Fe
alloys annealed and water quenched. The data show a change in transition
temperature from below room temperature to above in the range from
350 to 450 ppm total carbon plus nitrogen plus oxygen. These workers
also showed that the impact transition temperature increases with the second
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42 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

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44 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

phase content, and they proposed that increasing amounts of second phase
inhomogeneously distributed throughout the matrix, particularly at the
grain boundaries, lower the effective surface energy of a crack to promote
cleavage failure and brittleness.
Baerlecken et al [2], Demo [54], Semchyshen et al [60], and Plumtree
et al [57] all conclude from their data that the so-called high-temperature
embrittlement phenomenon of high-chromium ferritic stainless steels is
due to precipitation of chromium-rich carbides and nitrides caused by
relief of supersaturation when the alloys are exposed to high tempera-
tures. Baerlacken et al and Semchyshen et al find the embrittlement
occurs because the chromium-rich precipitate forms on grain boundaries,
while Demo and Plumtree claim the embrittlement occurs because a finely
dispersed precipitate in the grain matrix hinders dislocation motion, and
precipitates in the grain boundaries do not necessarily indicate alloy em-
brittlement. Perhaps the difference in thought resides in testing severity.
A grain boundary precipitate may be detrimental to the high-rate energy
absorbing requirement of the impact test but perhaps not detrimental to
the slow-rate energy absorbing requirement of the tensile or slow bend
test. The important point, however, is the general agreement that the
high-temperature embrittlement phenomenon observed in ferritic stainless
steels is dependent upon the levels of carbon and nitrogen in the alloys.
The embrittlement problem in chromium-iron alloys will manifest itself
whenever alloys containing moderate or high interstitial levels are heated
to temperatures above about 950 °C. The embrittlement is caused by pre-
cipitation of chromium-rich carbides and nitrides on grain boundaries or
dislocations or both. It is at once apparent that the same precipitation
mechanism causing embrittlement also produces the serious loss of cor-
rosion resistance when ferritic alloys are heated to high temperatures.

Notch Sensitivity in Annealed Alloys

Unlike the austenitic stainless steels, annealed chromium-iron stainless
steels are highly notch sensitive in a manner similar to mild and low alloy
steels [25,63,64]. In 1935, Krivobok [65] showed that the room-tempera-
ture impact resistance of chromium-iron alloys in the presence of a notch
declined sharply when the chromium content exceeded about 15 percent,
and this decline in properties was independent of carbon content in the
range of 0.01 to 0.20 percent. These data are shown in Fig. 25. Heger [66]
did a comprehensive study of the effects of notching on the tensile and
impact strength of annealed air-melted 27Cr-Fe alloys measured at room
temperature and at elevated temperatures. These data were reported by
Newell in 1946 [24]. Looking first at the effect of a notch on tensile properties,
Heger showed that the tensile strength increased and the elongation de-
creased in the presence of a notch. These effects are shown in Fig. 26 for

Atomic Per Cent Chromium

4.S 6.4 S.6 10.7 je.s v}.9 7P.O rg.r 21.2 23.3

e 10 12 74 76 76 20 22
Weight Pen Cent Chromium

FIG. 25—Effect of variation in chromium and carbon content on notch impact toughness
of commercial chromium stainless steels [65].

TEMPERATURE "C
0 200 400 600
/a?

/CO

•s >^

yse I 1 1 rr^-^
ay Elongation In ^Ini^ i ~.,

3
o zoo 400 600 BOO 1000 1200
Temperature, °/f
FIG. lA—Effect of a notch on the short-time, high-temperature tensile properties of
27Cr-Fe air-melted alloy [25,66].

short time tests run from room to elevated temperature. The difference in
tensile and elongation properties between notched and unnotched speci-

mens remained, even up to temperatures of 426 to 538 °C. When Heger

considered the effect of a notch on the impact resistance of a 27Cr-Fe
alloy, he found a surprising difference in the impact energy absorbed be-
tween the notched and unnotched specimens. Similar to Krivobok's data,
the notched specimen showed low impact energy absorption, but the un-
notched specimen had high impact energy absorption. These data from
Heger's work are shown in Fig. 27 along with the effect of testing tem-

TEMPERATURE "C
200 400 600 800
soo 1 1 1 1 1 1 1 1

250 E
- ^ ^ (-No Notch >
^ ISO

H^^- ""^^^ (
^**N^,^
200

1
150

•C. 80 1
<n
100
A -iizr
^
f^Full Notch
40
1-60 o

0
y
200 400 600 800 lOOO 1200 I400 1600
c

Temperature. "F

FIG, 27—Effect of temperature on impact properties of 27Cr-Pe, air-melted alloy. No

notch versus full notch [25,66].

perature. There is a wide difference in the energy absorbed between the

unnotched and notched specimen at room temperature which persists up
to about 870°C testing temperature. However, the magnitude of the dif-
ference in impact absorption energy between the two types of specimens
decreases as temperature increases because the impact absorption energy
for the unnotched specimen declines and increases for the notched speci-
men. At temperatures of 870 °C and above, the alloy was no longer notch
sensitive. These data indicate the value of preheating air-melted chromium-
iron alloys to reduce notch sensitivity in severe forming operations.
Based on data from Krivobok and Heger, it was generally believed into
the late 1940's that notch sensitivity occurred independent of carbon and
nitrogen content [63,67] and, in fact, was associated with the high-chro-
mium content of the alloys per se. Later work by Hochmann [68] and
Binder and Spendelow [69] showed that notch sensitivity in annealed
chromium-iron alloys with high-chromium levels was again basically

caused by the presence of critical levels of interstitial elements, particularly

carbon, nitrogen, and oxygen. The dramatic effects of interstitial level on
the impact behavior of annealed chromium-iron alloys were discovered
when vacuum melting techniques were developed and used to produce
alloys with extremely low interstitial levels.
The impact strength measured at room temperature of vacuum-melted
chromium-iron alloys as a function of chromium content is shown in Fig.
28 from Binder et al [69]. The maximum interstitial content of the alloys

120 o
140
5 100
I
120
u_
^- 80 100
^ 60 80 ^
in

i
Q.
E
•D
40

20 zz=_rzi 60

20
m
v>

0
0 10 20 30 40 50 60 70
Chromium %

FIG. 2S—Impact strength of vacuum-melted chromium-iron alloys [69].

used to generate these data include carbon 0.015 percent, nitrogen 0.01
percent, and oxygen 0.04 percent. As shown in Fig. 28, the toughness of
these high-purity alloys increases as chromium content is raised, reaching
a maximum at about 26 percent chromium, where unheard-of impact
strength values of 100 ft lb (136 J) are apparent. In contrast to Krivobok's
data, [65] (Fig. 25) which showed a sharp drop in impact strength for
alloys containing more than about 16 percent chromium, use of the vacuum
melting process has raised the level of chromium, for which excellent
impact toughness may be obtained in the presence of a notch from 16 per-
cent to somewhat greater than 35 percent. The key to this difference in
impact performance between normal air-melted steels and vacuum-melted
alloys is primarily in their carbon and nitrogen content. The relationship
between interstitial content and chromium content on toughness was de-
termined in a very comprehensive investigation by Binder and Spendelow
[69], as shown in Fig. 29. At chromium levels above about 15 to 18 per-
cent, there is a drastic decrease in the carbon and nitrogen levels tolerable
in a high-chromium alloy for high room-temperature impact resistance.
For an air-melted steel with carbon and nitrogen contents up to about

0.15
;1
'" c
1 1
•
•
•
I
1 o^
1 -
1
1 •
-l
010 o <•
« •

» o
o
o
t
•
o
oo o
J?
i- o
o o
o

n
00°
o
o
4' OO o c
§"
a

20 30 40
Chromiunn %

FIG. 29—Influence of carbon and nitrogen on toughness of chromium-iron alloys. Open

circles: high-impact strength alloys; solid circles: low-impact strength alloys [69].

0.12 and 0.05 percent [69], respectively, these data would predict good
room-temperature impact resistance is possible only if the alloys contain
chromium levels below 15 to 18 percent. The agreement with Krivobok's
early data [65] on air-melted alloys is excellent, but the conclusion that
poor impact resistance was due to chromium content per se was incorrect.
The low impact resistance of Krivobok's alloys containing more than 15
to 18 percent chromium was not caused by the chromium level but was
due to the high interstitial levels characteristic of air-melted steels.
Binder and Spendelow, in their comprehensive investigation, also de-
termined the individual effects of carbon and nitrogen on impact resistance
of annealed alloys at two levels of chromium, 18 and 25 percent. These
data are tabulated in Figs. 30 and 31, respectively. Both figures show:
(a) that a straight line of a 45-deg slope may be drawn to separate the
areas of high and low toughness, (b) that there is an equivalency in the
effect by carbon and nitrogen on toughness, (c) that the carbon plus nitro-
gen sum is critical rather than the absolute value of each separately, and
(d) that the maximum sum of carbon plus nitrogen tolerable for good
room-temperature toughness is 0.055 percent for 18 percent chromium
and 0.035 percent for 25 percent chromium.
Until the late 1960's, achieving levels of 0.035 percent and lower was
possible only in the laboratory. With the development of economical
vacuum melting and vacuum and gas refining techniques, commercial
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DEMO ON FERRITIC STAINLESS STEELS 49

024 0
•
" •

020

•
o

016

« •
a
•a a
0.12
a
a 4 <
V 9 A

008 "^
^ i
<
0 aa

• <^ - :
0.04 X a 'o

••
/ ^
s° • , * A
•
A ••
•
•
0 o
0.04 0.08 0.12 0.16
Corbon %

FIG. Vi—Effects of carbon and nitrogen on toughness of 17 to 19Cr-Fe alloys. Open

circles: high-impact strength alloys; solid circles: low-impact strength alloys; semi-solid
circles: intermediate impact strength alloys; triangles represent commercial arc-melted steels
[69].

production of high chromium-iron alloys became feasible and a reality.

These alloys, to be described later, show excellent toughness at room tem-
perature in the presence of notches. However, for available air-melted
alloys such as AISI Type 430 (18 percent chromium), Type 442 (20 per-
cent chromium), and Type 446 (26 percent chromium), notch sensitivity is
a factor of major importance which must be considcied carefully in appli-
cation of these alloys. Good engineering practices require avoiding surface
scratches and reentrant angles, notches, or other forms of stress risers
when these air-melted alloys are used under shock loading conditions.

Weldable, Corrosion-Resistant, Ductile Ferritic Stainless Steels

The largest single drawback to the use of ferritic stainless steels has
been the loss of corrosion resistance and ductility following exposures
to high temperatures, as in welding and isothermal heat treatments. The
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of Washington I M International
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50 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

014 •
• _ \ _
012
•
010 - -J -.-
••
008
•• • 1 t
006 • 1 I

004
• ' • • : 1I '
002 ^
•
0 • i •
0 002 004 006 0 0 8 010 012 0J4
Carbon- %

FIG. 'il—Effects of carbon and nitrogen on toughness of 24 to 26Cr-Fe alloys. Open

circles: high-impact strength alloys; solid circles: low-impact strength alloys [69].

Other problems with ferritic stainless steel (475 °C and <T-phase embrittle-
ments) can be tolerated because relatively long exposure times at moderate
temperatures are required to cause these other embrittling problems.
However, unless a material has good corrosion resistance and ductility in
the as-welded condition, its usefulness as a material of construction is
limited severely. As just described, the cause for the serious loss in ductility
and corrosion resistance when ferritic stainless steels are exposed to high
temperatures and for the notch sensitivity of annealed alloys is related to
the interstitial content of the alloys. After research in the early and mid-
1960's had shown this fact, the research effort in the late 1960's saw
development and commerciaUzation of weldable, corrosion-resistant
chromium-iron alloys. To reach this position, three routes to achieve
interstitial control were researched and developed. Demo [70] has sum-
marized and described these methods used to achieve interstitial controls
in ferritic stainless steels.

Low Interstitials
By reducing the interstitial levels below certain minimum values, weld-
able and corrosion resistance can be produced, as shown in the works of
Hochmann [68], Demo [70], Bond [53], Streicher [56], and Hodges [43,55].
Binder's [69] (Fig. 29) early work showed how the impact resistance of
annealed ferritic stainless steels varied with interstitial and chromium
content. A similar type of study by Demo [70] showed the relationship of
interstitial level and chromium content on the ductility and corrosion re-
sistance of as-welded alloys. These data are summarized in Fig. 32 and
include a comparison to Binder's data for impact resistance on annealed

specimens. The carbon and nitrogen levels which can be present in an

alloy without affecting the weldability of a chromium-iron alloy are low
and decrease rapidly with increasing chromium content. As can be seen
from the data in Fig. 32, the interstitial tolerance level for a "good" as-

BINDER etaMREF 69)

•LIMITS FOR ANNE&LEO
IMPACT RESISTANCE

LIMITS FOR AS-WELDED

DUCTILITY a INTERGRANULAR
CORROSION RESISTANCE

24 28 32
% CHROMIUM

FIG. VL—Effects of carbon and nitrogen level and chromium content on as-welded ductility
and intergranular corrosion resistance of chromium-iron ferritic stainless steels. Comparison
to Binder's limit for impact resistance of annealed specimens [70].

welded specimen at a given chromium level is lower than that needed for
impact resistance of an annealed specimen. Demo further studied the
variation in the properties of weld ductility and weld corrosion resistance
as functions pf chromium content and interstitial sum level. These data
are tabulated in Table 8. As chromium content increases from 19 to 35

TABLE 8—Carbon plus nitrogen limits for as-welded properties of

intergranular corrosion resistance and ductility as a function of
chromium content.

Limit for Sum of C + N (ppm) to Have the

Indicated Property in an As-Welded Alloy"

Chromium Level, % Intergranular'

by weight Corrosion Resistance Ductility'
19 60 to 80 >700
26 100 to 130 200 to 500
30 130 to 200 80 to 100
35 --250 <20
NOTE—Data by Demo 170\,
"Sample thickness: 0.1 in, (2.54 mm) thick.
'Intergranular corrosion resistance in bpiling ferric sulfate-50%
sulfuric acid solution,
'No cracks, as determined by bending around a 0.2-in. mandrel.

percent, the amount of carbon plus nitrogen that can be tolerated for
intergranular corrosion resistance increases somewhat. Conversely, for as-
welded ductility, the sum of tolerable interstitials is reduced drastically.

At low chromium levels, as-welded corrosion resistance is the factor con-

trolling whether an alloy has good weldability; at high-chromium levels,
as-welded ductility is the limiting factor. At the 26 percent chromium
level, intergranular corrosion resistance is more sensitive to the interstitial
sum level than is ductility while at 35 percent chromium; the as-welded
ductility is more critically dependent on the interstitial sum than is cor-
rosion resistance.
To produce weldable and corrosion-resistant chromium-iron alloys by
this route, it is evident that very low levels of carbon and nitrogen are
needed. Until recently, such low levels could only be produced in a labora-
tory or by using high-purity raw materials. However, technological ad-
vances in steel-making practices have made the concept of low interstitial
ferritic alloys possible through the development of such techniques as
oxygen-argon melting, vacuum refining, and electron-beam refining. Of
particular note is the electron-beam continuous hearth refining technique
developed by Airco Vacuum Metals and described by Knoth [71]. This
process has the advantage of achieving the lowest carbon and nitrogen
levels by exposing a high surface to volume ratio of molten metal to a
high vacuum for extended periods of time. As the molten metal flows
down a series of water-cooled copper hearths, electron beam heat sources
provide localized regions of intense heat in the molten metal, causing
volatilization and removal of tramp impurity elements. The process is
being used currently to produce commercially a high-purity ferritic stain-
less steel containing nominally 26 percent chromium, 1 percent molybde-
num, and balance iron. By maintaining the carbon plus nitrogen level
below 250 ppm, it is reported [72,73] that this commercially available al-
loy is ductile and corrosion resistant following welding, has good tough-
ness, and combines resistance to stress-corrosion cracking with good gen-
eral corrosion and pitting resistance. However, for a weldment to be re-
sistant to intergranular attack, a carbon plus nitrogen sum level at or near
250 ppm is too high. Demo [45] reports intergranular attack on a high-
purity 26Cr alloy containing 180-ppm carbon plus nitrogen, while Streicher
[59] (Table 2) shows grain dropping in the weld and heat-affected zone of
two high-purity 26Cr-lMo alloys containing 105 and 230-ppm carbon plus
nitrogen, respectively. For complete resistance to intergranular attack
following welding or isothermal heat treatment, it appears that the carbon
plus nitrogen levels in 26Cr and 26Cr-lMo high-purity alloy systems must
be maintained below about 100 to 120 ppm [70] with nitrogen [59] less
than 90 ppm. The high-impact values at and below room temperature for
an electron beam refined 26Cr-lMo alloy as compared to a 26Cr-lMo al-
loy containing 0.08 percent carbon is remarkable, as shown in Fig. 33 [60,
72]. The scatterband in the E-Brite 26-1 alloy data is the result of speci-
men orientation, variations in thermal treatments, and cooling rates.

-50 0 50
TEST TEMPEFlATURE{Of.)

FIG. 33—(a) Charpy V-notch transition temperature range for commercially produced
electron-beam-melted ferritic steel containing 26 percent chromium and 1 percent molybdenum
(E-Brite 26-1) [72]. (b) Transition curve for quarter-size V-notch impact specimens of an
air-melted steel containing 26 percent chromium and 1 percent molybdenum [60].

Interstitial Stabilization
A second means to control interstitials is to add elements to the alloy
which form stronger carbides and nitrides than does chromium. Such
elements include titanium, columbium, zirconium, and tantalum. The
early work by Lula, Lena, and Kiefer [48\ describes a comprehensive ef-
fort to study the intergranular corrosion behavior of ferritic stainless
steel, including the effects of titanium and columbium additions. These
investigators showed that titanium and columbium additions were not
completely effective in preventing sensitization when the alloys were sub-
jected to high temperature. This result was caused by not considering the
need to tie up nitrogen as well as carbon and also by the unknown fact at
the time that titanium carbide itself is dissolved in highly oxidizing solu-
tions such as the boiling nitric acid solution used in the study.
More recent work by Baumel [74], Bond and Lizlovs [52\, and Demo
[75,76] have shown that columbium and titanium additions were effective
in preventing intergranular corrosion following exposure of ferritic stain-
less steels to high temperatures such as isothermal heat treatments and
welding. To resist intergranular corrosion, titanium additions of about six
to ten times the combined carbon and nitrogen level are necessary; for
columbium, additions of eight to eleven times are required. The relation-
ship of interstitial content, chromium level, and titanium level for inter-
granular corrosion resistance and ductility after welding has been studied
extensively by Demo [75.76]. Bond et al [52], Lula et al [48], Herbsleb
[77], Baumel [74], and Cowling et al [78] have shown that titanium-stabi-
lized alloys may show intergranular attack when exposed to a highly
oxidizing solution such as boiling nitric acid due to dissolution of tita-
nium carbonitrides; however, columbium-stabilized alloys resist inter-
granular attack even in highly oxidizing solutions.
Demo [75,76], Semchyshen et al [60], Wright [79], and Pollard [80]
have reported the effects of stabilizing additions on the weld ductility of
ferritic stainless steels. By introducing titanium or columbium in the fer-

ritic alloy, the level of interstitial which can be present in the matrix with-
out adversely affecting the room-temperature ductility after welding is
increased significantly. These data are shown in Table 9 by the tensile
ductility measurements on welded 18Cr-2Mo specimens [60] and in Table
10 by the slow bend tests on welded 26 to 30Cr alloys [75,76,79]. With
TABLE 9~Ef/ect of stabilizer additions on the tensile ductility of
annealed versus welded specimens containing 18% chromium-2%
molybdenum.

Elongation in 50 mm, %
c + N, % bv Ti or Cb, %
weight by weight Annealed As Welded

0.005 0 33 31
0.03 0 3] 8
0.07 0.5 34 30
0.06 0.6 28 21

NOTE—Data by Semchyshen et al [60].

TABLE 10—Effect of titanium on the as-welded bend ductility for

chromium-iron ferritic stainless steels containing 26 to 30% chromium.

C + N, ppm Ti, % by weight Bend Test Ductility As-Welded

113 0 passed 180 deg, 2t°

310 0 passed 180 deg, l/2t''
362 0 failed 90 deg, 2t°
450 0 failed 90 deg, 21°
900 0 failed 135 deg. I t '
300 0.22 passed 180 deg, l/2t°
387 0.24 passed 180 deg, 2t°
488 0.47 passed 180 deg, 2t°
850 0.45 passed 180 deg, 1/2^

"Data by Demo [75,76\, 0.1-in.-thick specimens, t = specimen thickness.

'Data by Wright [79\, 0.06-in.-thick specimens.

stabilizer additions, the interstitial elements are effectively tied up as

stable carbides and nitrides such that their effective level in solid solution
is reduced. Consequently, stabilized alloys at relatively high levels of
carbon and nitrogen act similarly to the very low interstitial alloys just de-
scribed in having excellent corrosion resistance and ductility (tensile or
bend) following exposure to high temperatures which, without stabiliza-
tion, would cause loss of corrosion resistance and ductility.
The effects of stabilizing additions on the impact properties of chromium
iron alloys in comparison to the impact properties of low interstitial al-
loys, however, presents another story. The effects of stabilizing additives
on impact properties have been studied and described by Semchyshen et al

[60] and Wright [79]. Two aspects have been studied, namely, the effect
of titanium content and interstitial level on the impact resistance of (a)
annealed specimens and (b) specimens heated to high temperatures by
welding or isothermal heat treatments. In the annealed condition, the
titanium-modified steels exhibit transition temperatures commensurate
with their interstitial levels; that is, whatever the impact transition tem-
perature is for the unstabilized, annealed alloy as a function of interstitial
level (see Fig. 29), remains about the same or is slightly reduced when the
alloy is stabilized.
Stabilizing additions of titanium, however, are useful in reducing the
detrimental effects of high-temperature treatments on the impact resistance
of high interstitial alloys. These effects of stabiUzing additions taken from
Semchyshen et al [60] are shown in Fig. 34 for air-melted commercial

a
100 --

\b-U50'C
60 —
- N. Ti-1150*C

20 - D
^^D_____S- • Nb-815'C
D
-20
Ti-815"G

-60 --

-100 1 1 ! 1
0 0-2 0-4 0-6 0-8 10
Titanium or niobium c o n t e n t ( wt%)

FIG. 34—Transition temperatures for quarter-size Charpy V-notch specimens air-melted

commercial-purity 18Cr-2Mo steels water quenched from 11S0°C {sensitized) and 815°C
(annealed) as a function of titanium or columbium content [60].

purity (0.07 percent carbon plus nitrogen) 18Cr-2Mo alloy. Increases in

titanium content from 0 to 0.8 percent show little effect on the impact
transition temperature of annealed (815 °C) specimens. However, increases
in titanium content from 0 up to about 0.5 percent improve (lower) the
transition temperature when the alloys are subjected to a high-tempera-

ture treatment (1150°C). These data also show that columbium additions,
though effective in lowering the transition temperature for alloys sub-
jected to a high temperature, were somewhat harmful to the impact re-
sistance of the alloys in the annealed condition. Semchyshen et al [60] also
showed that titanium additions beyond about ten times the combined
carbon and nitrogen content could affect (increase) the impact transition
temperature of annealed 18Cr-2Mo alloys (0.07 percent carbon plus nitro-
gen) as shown in Fig. 35. A precipitation of an intermetallic phase markedly
increased impact transition temperatures.

200

20
-150
0-81% Ti

15 0-47% Ti
c
100 c
r
10
m
(A

^ 5 - 50
p,^—O 1-27% Ti
^^/^;^_^I-86%Ti

-50 0 50 100
Test temperature i'C)

FIG. 35—Transition curves for qitarter-size Charpy V-notch impact specimens of air-
melted 18Cr-2Mo; 0 to IMTiferritic stainless steels heat treated at 815 °C for 1 h and water
quenched (60].

Superimposed on the effects of titanium and interstitial content on the

ductility and impact resistance of chromium-iron alloys is the marked
effect of thickness on these properties, particularly impact resistance. This
point is shown by the data in Table 11 taken from Wright's work [79]. In
order to have acceptable properties (weldability and touchness) at plate
gages as heavy as 0.5 in., interstitial sum level in a 26Cr alloy must be
as low as or lower than about 100 to 125 ppm. For alloys containing about
3(X) to 900 ppm total carbon and nitrogen, toughness may be poor at
gages above about 0.13 in., and weldability is poor at all gage thicknesses.
The addition of titanium increases the thickness or gage level at which

TABLE 11—Impact transition temperatures as a function of gage and added titanium

for annealed 26Cr-IMo alloys.

Gage Thickness, in. (mm)

Charpy V-Notch, Ductile to Brittle Temperature, °C

0.12 to 0.14
C + N, % by weight 0.5 (12.7)° (3.05 to 3 .56)- • 0.06(1.52)''

0.0065 -57 -73

0.0310 149 38 -73
0.0900 162 38 -18
0.0300 + 0.22 Ti 121 -1 -46
0.0850 + 0.45 Ti 107 38 -46

NOTE—Data by Wright [79].

"Water quenched after anneal.
'Air cooled after anneal.

an alloy will have good weldability. For example, as Wright notes, a

26Cr-lMo alloy containing 300 ppm total carbon and nitrogen and
0.22 percent titanium, has excellent toughness and weldability (that is,
as-welded ductility and corrosion resistance) up to a gage thickness of
about 0.13 in.
In summary, adding a stabilizer to an alloy of moderate carbon and
nitrogen will not improve the annealed impact behavior significantly but
may improve the as-welded ductility and corrosion resistance tremendously.
This point is a most important difference between stabilized alloys and
low interstitial alloys. The high-purity material will have excellent tough-
ness and as-welded corrosion resistance and ductility. The stabilized ma-
terial will also have excellent as-welded corrosion resistance and ductility
but may not have high room-temperature impact resistance. These effects
as shown by Wright [79] are particularly magnified at section thicknesses
greater than about % in. Therefore, for thick plate sections where high
room-temperature toughness is an absolute requirement, the low inter-
stitial alloys would be acceptable, but the stabilized grades would not. On
the other hand, for thin material, as required in heat exchanger tubing,
the titanium stabilized alloys and the low interstitial alloys have similar
toughness and weldability properties so that either alley system may be used.

Weld Ductilizing Additions

A third method which produces high chromium-iron ferritic stainless
steels with good as-welded ductility is to add low concentrations of selec-
ted elements with atomic radius within 15 percent of the « matrix. This
method was developed and investigated extensively by Steigerwald et al
[81\. As noted in Fig. 32, the carbon and nitrogen level for as-welded

ductility is reduced drastically as chromium content increases. At 35 per-

cent chromium, an impossibly low interstitial level of about 10 to 15 ppm
is necessary for as-welded ductility. Steigerwald et al found that, in the
presence of low amounts of copper, aluminum, vanadium, and combina-
tions of these elements, alloys with good as-welded ductility could be pro-
duced at high interstitial levels. A summary of this work is shown in Fig.
36. With selective additives, an alloy containing 35 percent chromium can

FIG. Id—Effect of weld ductilizing additives on as-welded ductility and corrosion resistance
of high chromium-iron stainless steels; additives, singly or in combination, include aluminum,
copper, vanadium, platinum, palladium, and silver in a range O.I to 1.3 percent [81].

be produced with both as-welded ductility and corrosion resistance at

interstitial levels of 250 ppm versus the 10 to 15 ppm level needed at
this chromium level when the additives are absent. It is remarkable that
a ferritic stainless steel containing 35 percent chromium can be made with
as-welded ductility at intermediate interstitial levels.

Sigma Phase and 475 °C Embrittlement Susceptibility

By the techniques of interstitial control, chromium-iron alloys can be
produced which resist the damaging loss of corrosion resistance and
ductility following high-temperature exposures, as in welding or iso-
thermal heat treatments. In addition, some alloys can be produced to also
have high room-temperature impact toughness in thick sections. There-
fore, by interstitial control methods, the high temperature exposure and
notch sensitivity problems which have limited severely the usefulness of
ferritic stainless steels before have been removed. However, though not as
serious as the embrittling problems described earlier, the 475 °C and <T-
phase embrittling phenomenon will still occur in alloy composition made
resistant to high-temperature exposure effects. This point has been shown
by works of Grobner [42], Hochmann [44], and in reported data for E-
Brite 26-1 [72].
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DEMO ON FERRITIC STAINLESS STEELS 59

Molybdenum Additions
For improving the general corrosion and pitting resistance of chro-
mium-iron stainless steels, the effects of molybdenum additions have been
extensively studied and reported on by Bond [82], Demo [70], Streicher
[59], and Steigerwald [83-85]. Of particular note here is the effect of
molybdenum additions on embrittling a chromium-iron stainless steel.
Semchyshen et al [60] have summarized the data describing the effect
molybdenum level has on the toughness of 18 and 25Cr alloys. The effects
of molybdenum level on the impact transition temperature of an annealed
25Cr alloy containing high and low interstitials, respectively, are shown
in Fig. 37. There is considerable difference in the impact transition
temperature of the high-purity alloys (-50°C) and the high interstitial
alloys ( + 50°C) without molybdenum addition, as described earlier. The
point, however, is that molybdenum additions up to about 2 to 3 percent
have little effect on toughness but an adverse effect when the molyb-
denum level exceeds about 3 to 4 percent. This decrease in toughness as-
sociated with high-molybdenum contents is caused by the formation of
chi (X) phase, a brittle intermetallic compound of iron, chromium, and
molybdenum.
Streicher [86] has reported on a study of the effects of heat treatment
on the microstructure and formation of x and a phase in two low inter-
stitial alloys containing 28 percent chromium-4 percent molybdenum and
28 percent chromium-4 percent molybdenum-2 percent nickel. One-hour
heat treatment in the range of 700 to 925 °C produced only a small
amount of ^ at the grain boundaries. The largest amounts of a are formed
by heating at 815 °C. Heating for 100 h at 815 °C caused <r and large
amounts of X phase to form a grain boundaries and within the grains.
The complex relationship between chromium, molybdenum, and iron
levels on the formation of x and a phases has been described in detail by
the work of McMullen et al [87]. The ternary phase diagram for the iron-
chromium-molybdenum system at 898 °C (1650°F) isotherm, as defined by
McMullen et al, is shown in Fig. 38 [87]. x phase is stable over a wider
temperature range than <^ [87], so annealing above 980°C is required to
eliminate it in steels with 18 percent chromium and over 3.5 percent
molybdenum [60] and in steels containing 28 percent chromium-4 percent
molybdenum [86].
For 26Cr alloys containing 1 percent molybdenum and stabiUzed with
titanium, Aggen [SS] and Demo [89] have shown that a corrosion-damag-
ing second phase occurs in the alloy when a slight excess of titanium
beyond that needed to tie up the interstitials is present. This phase, be-
lieved also to be x, is richer than the matrix in titanium, molybdenum,
and silicon and forms by isothermal holds for extended periods in the
temperature range from 595 to 850°C. Before it has grown large enough
to be seen by an optical microscope, the intergranular corrosion resistance
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60 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

JOULES
i
3-^

(jUia/uiSif) X8J»U3 t^vdtuj

I
if
JOULES

IS
III
(jUlD/Ul!il() AKjaUS JOHClUJ]
4
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STP619-EB/Jan. 1977

DEMO ON FERRITIC STAINLESS STEELS 61

20 30 40 50 60
Weight % Chromium

FIG. 38—Constitution of iron-chromium-molybdenum alloys at 898°C {1650°F). « =

Sigma; x = chi;andf = Fc/Afos [87].

of a susceptible alloy will be affected deleteriously when it is exposed to

highly oxidizing solutions. The effect only appears in alloys containing
molybdenum and excess titanium and can be removed by short annealing
treatments at temperatures above about 900 °C.

Summary
Chromium-iron alloys are bcc up to the melting point. Therefore,
hardening by the ferrite-austenite mechanism upon heating and quenching
cannot occur. Ferritic chromium iron alloys can be embrittled by the
phenomenon of 475 °C embrittlement, ir-phase embrittlement or x-phase
embrittlement for those alloys containing molybdenum. These em-
brittling mechanisms generally require a long-time isothermal treatment or
very slow cool through the intermediate temperature regions such that
they do not normally constitute a threat to the weldability and processing
of ferritic stainless steels. The serious loss of ductility and corrosion re-
sistance when ferritic stainless steels are subjected to high-temperature
exposures as in welding or isothermal treatment and the problem of notch
sensitivity have been shown to be related to interstitial levels in the
alloys. By development of interstitial control techniques, it is now possi-
ble to produce high-chromium ferritic stainless steels which are corrosion

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62 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

resistant and ductile following a high-temperature exposure, as in welding

or an isothermal heat treatment. Further, depending on the interstitial
levels, high chromium-iron alloys can be produced, having excellent
toughness and impact transition temperatures below room temperature.
By making chromium-iron stainless steels weldable and tough, and
combining this property with stress-corrosion resistance and good general
corrosion resistance, attractive new materials of construction are and will
be available to compete with austenitic 18Cr-8Ni-type stainless steels.
Several organizations throughout the world are engaged in commercial
development of ferritic stainless steels. An 18Cr-2Mo alloy stabilized with
columbium or titanium is being produced in Europe. A comprehensive re-
view article on the properties of ISCr-type ferritic alloys has been
published by Schmidt and Jarleborg [90]. Where greater corrosion re-
sistance is desired, several new compositions are either in commercial
production or are being actively developed. These include a 26Cr-lMo
alloy produced either with extremely low interstitial levels by electron-
beam melting techniques or with moderate interstitial levels stabilized
with titanium and, to a lesser extent, with columbium. In commercial de-
velopment are low interstitial alloys of the composition 26 percent chro-
mium-2 percent molybdenum, 21 percent chromium-3 percent molybde-
num, 28 percent chromium-2 percent molybdenum, 28 percent chromium-
4 percent molybdenum, 28 percent chromium-4 percent molybdenum-2
percent nickel. These alloys have better general corrosion resistance than
Type 316 stainless steel. Those like the 28Cr-4Mo and 28Cr-4Mo-2Ni
alloys have been shown by Streicher [59] to have corrosion resistance in a
variety of aggressive environments comparable or better than the highly
alloyed nickel-based alloys. The complex relationship between chromium
and molybdenum content on pitting resistance, ductility, and weld
ductility, as studied by Streicher [59] is shown in Fig. 39. As shown by

28 30 32
V;T. Vo CHROMIUM

FIG. i9—Properties of iron-chromium-molybdenum alloys. Pitting tests: 10% FeCl-

6H2O at 50°C {with crevices), 2 percent potassium manganate-2 percent sodium chloride
at 90°C. Stress corrosion test: 45 percent boiling {155°C) magnesium chloride on welded
U-bend specimens. Sulfuric acid: boiling 10 percent by weight. Carbon: 10 ppm; nitrogen:
200ppm; carbon plus nitrogen: 250ppm [59].
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DEMO ON FERRITIC STAINLESS STEELS 63

these data, the 28Cr-4Mo-type alloys have better resistance to pitting than
any other types of chromium-molybdenum-iron alloys now under devel-
opment. With a variety of desirable properties available, including good
weldability and resistance to stress-corrosion cracking, a family of ferritic
stainless steel compositions is becoming available as materials of con-
struction which will replace the austenitic and nickel-based alloys in
many appHcations.

References
[1] Bain, E. C. and Aborn, R. H. in Metals Handbook, 1948 ed., American Society for
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[2] Lecken, E. B., Fischer, W. A., and Lorenz, K., Slahl undEisen, VoL 81, No. 12, 1961,
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[3\ Colombier, L. and Hochmann, J., Stainless and Heat-Resisting Steels, Edward Arnolds
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[5] Newell, H. D., Metal Progress, April 1947, pp. 617-626.
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64 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

[28] Riedrich, G. and Loib, F., Archivfur das Eisenhuttenwesen, Vol. 15, No. 7, 1941-1942,
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STP 619-1977

Uploaded by

STP 619-1977

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STRUCTURE,

ASTM SPECIAL TECHNICAL PUBLICATION 619

List price $7.50

AMERICAN SOCIETY FOR TESTING AND MATERIALS

Reprinted by permission from the

Printed in Baltimore, Md.

Cleaning Stainless Steel, STP 538 (1973), $18.00 (04-538000-02)

Introduction to Today's Ultrahigh-Strength Structural Steels, STP 498

ASTM Committee on Publications

Copyright by ASTM Int'l (all rights reserved); Sun Dec

REFERENCE: Demo, J. J., Structure, Constitution, and General Characteristics of

2 GENERAL CHARACTERISTICS OF FERRITIC STAINLESS STEELS

and 30 percent chromium. The high chromium hmit is arbitrary and is

Structure and Constitution

Weight Percentage Chromium

FIG. 1—Chromium-iron phase diagram (IJ.

1. Chromium is a member of a group of elements called ferrite formers

Effect of Carbon and Nitrogen

DEMO ON FERRITIG STAINLESS STEELS 5

an expansion to 26 percent chromium is observed. In addition, the point

Strengthening by Heat Treatment

DEMO ON FERRITIC STAINLESS STEELS 7

• Single Phase cc '900

FIG. 5—Iron-chromium phase diagram in binary high-purity 25 la 76Cr alloys. This

DEMO ON FERRITIC STAINLESS STEELS 9

chromium-iron alloys. Fortunately, <T phase developed in an alloy may be

0 SOD 400 600 800 1000 1200 MOO I600

FIG. 8—Hardness surveys on bars after prolonged heating in a temperature gradient.

[24,26], using a 26Cr stainless steel, were able to show embrittlement on

Annealed Heated 4 h at 450 °C

"tsi = tons per square inch.

Colombier, after repeated heating in the range of 450 to 500°C, the

Chromium, % Brinell Chromium, % Brinell

14.5 150 20.1 260

NOTE—Data by Newell [5] and Riedrich and Loib [28].

110 i 1 I < ) 1 111

loys to hardness increases. Rapid increases in hardness with exposure

a phase -• transition phase -• <r phase

in the a matrix leading subsequently to gross precipitation of <^ phase

sam SCO too mo ne 30B am not

JB7NV SOB 100 700 ao SCO 1000 mo

FIG. 12—Phase diagram of the iron-chromium system according to Williams [37].

550°C in agreement with all experimental data. The mechanism of age

FIG. 13a—Electron micrograph of an extraction replica of bcc chromium-rich zones

FIG. 136—Transmission electron micrograph showing structure existing in a 47.8 atomic

on 475 °C embrittlement taken from Heger [50] are summarized in Table

I I I I lull I I I I mil I I I 1Mmil

*-J_ ••••' • ' • • • *••

I I I I m i | 1—I I I iiii[ 1—I I I iili| 1—I I I iiii| I—I I 11iw

2 100 —o—*- ooa

FIG. 14—Impact strength at room temperature of half-size Charpy V-notch specimens

The 475 °C embrittlement may be alleviated and toughness and corro-

Summary 475 °C Embrittlement

TABLE 2—Tensile properties at room temperature of a vacuum-melted and air-melted alloy

1 0 30.9 (213) 49.9 (344) 32.5

1 vacuum melted 17.4 0.002 0.0031

NOTE—Data by Grobner [42].

TABLE 3—Effects of composition on 475''C embrittlement in

Element Effect on 475 °C Embrittlement"

TABLE 4—Average rate of corrosion in boiling 65% nitric acid for

Condition Corrosion Rates, mil/year

NOTE—Data by Newell [25].

DEMO ON FERRITIC STAINLESS STEELS 21

embrittlement is caused by formation of coherent chromium-rich pre-

High-Temperature Embrittlement and Loss of Corrosion

2. Hochmann [44] also proposed the need for austenite formation at

High-Temperature Loss of Corrosion Resistance

Specimen' Corrosion Rate."

NOTE—Data by Demo [54].

poor corrosion resistance of specimens water quenched or air cooled from

Corrosion Rate, mm/dm^ day, for the average of 5

1450°F 1700°F 1900°F 2100°F

0.0021 0.0095 167 185 148 326

NOTE—Data by Bond [53].

sistance of a series of 17Cr alloys in boiling 65 percent nitric acid. Based

ship between heat treatment, the presence of an intergranular precipitate,

-J_ ••••' • ' • • • ••