Data shown is typical, and should not be construed as limiting or necessarily suitable for design.

Actual data may vary from those shown herein.

Technical Data Sheet

Bright Annealing

Oxygen concentrations are critical whether

measured in terms of dew point, which is
the custom for annealing in hydrogen or
argon atmospheres, or as measured on a
partial pressure scale, which is the custom
for vacuum annealing. Austenitic stainless
tubing in such an atmosphere can be
heated to above 1900F (1038C) to
dissolve carbides and relieve residual
stresses. In such an atmosphere at peak

Temperature,
Temperature, F F

-40

-140

3500

Pa

103

102

O3
Cr 2
MO
MO

RE

-50

RE

OX
ID

IZIN

RE

-60

DU

CIN

O
Mn

Torr

101

10-1

100

10-2

10-1

10-3

10-2

10-4

TiO

-90

Ba
100

101

gO

O3
AI 2
O 2

-100
500

1000

100

VO

B 2O

SiO 2

O5
Ta 2
bO

-70
-80

-120

3000

IS MORE
DIFFICULT TO
REDUCE THAN
THOSE PLOTTED

-20
-30

-100

2500

-10

-40

-80

Sn, Os,
Bi

-20

-60

2000

METALS EASIER TO REDUCE

THAN THOSE PLOTTED:
Au, Pl, Ag, Pd,
Ir, Cu, Pb,,
La
Co, Ni,

2O

+20

1500

1500

O
Ce eO
B

ThO 2

Partical Pressure of Water Vapor

+20
+10

+40

1000

Na

+60

+30

500

+80

+40

100

Mo
O
WO 2

+100

FeO

ZnO

For bright annealing to be effective, tube

surfaces must be clean and free of foreign
matter. The annealing atmosphere must
be relatively free of oxygen (if a bright
result is desired). This is accomplished
by removing nearly all gas (creating a
vacuum) or by displacement of oxygen and
nitrogen with dry hydrogen or argon. For
common stainless steel alloys, the minimum
atmosphere quality required is about -40F
(-40C) on a dew point scale (for hydrogen
or argon atmosphere) or less than 10-1
Torr partial pressure of water (for vacuum
annealing).

temperature, oxides will be minimal. Best results can be obtained by

heating as rapidly as feasible. Slow heating will result in oxidation
at intermediate temperatures. Higher peak temperatures produce a
more reducing condition and a brighter final appearance.

Dew Point of Hydrogen

Annealing is a critical production step. If

performed poorly, metal surfaces can be
rendered stained, pitted, or cracked, and the
metal susceptible to corrosion. Corrosion
damage may be revealed in a number of
ways, from stress corrosion cracking to
intergranular attack or general corrosion.
Any number of contaminants left on the
tubing surface can and will cause damage
during heat treatment. This article attempts
to address a number of misconceptions that
exist about annealing and bright annealing,
in particular. Sensitization and carbide
stabilizing anneals are also addressed.

10-5

2000

Temperature, C C
Temperature,

Furnace soak time is not particularly critical for stainless solution

annealing. An old rule of thumb for soak time is an hour per inch
of section thickness. Using this as a guide, 0.065 inch thick tubing
should soak for 4 minutes at temperature. Fast cooling is critical
for corrosion resistance; slow cooling can result in sensitization
and diminished corrosion resistance. Slow cooling also subjects
the product to a more oxidizing condition (generally not desirable).
The metallurgy of bright annealing has been reasonably well defined
for some time. In order to achieve a bright result, the most stable
oxide forming element in an alloy in any significant concentration
must be reduced at peak temperature and atmosphere quality rather
than oxidized. For the common austenitic stainless alloys such as
304L and 316L, the most stable oxide former present in significant
concentrations is chromium. As such the oxidation potential of
chromium at peak annealing temperatures and atmosphere quality

Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein.

will largely determine whether the stainless

will be bright. The previous figure is a Metal
Metal Oxide Equilibria diagram in pure
hydrogen atmospheres.1 The lines on this
diagram show where the oxidation reaction
is approximately equal to the reducing
reaction. To get a bright result you will
need to be a little hotter and/or better
in atmosphere quality. If an atmosphere
condition exists which is below and/or to
the right of an equilibrium line of relevance,
the condition is a reducing one, where little
oxide should exist on the surface. When
the opposite condition exists for chromium,
oxidation of chromium will be favored. From
this diagram it can be seen that in order
to reduce Cr2O3, temperatures higher than
1850F (1010C) are needed at a dew
point of -40F or lower. Please note that
this diagram also explains nicely why slow
heating or cooling is undesirable if a bright
surface finish is desired.
Well-maintained industrial hydrogen or argon
furnaces can typically achieve operating dew
point levels in the range of -40 to -50C
(-40 to -58F). It should be noted that
depending on the alloys being annealed, this
quality level may or may not be necessary.
Typically, hydrogen or argon can be throttled
to some extent to achieve the quality of
atmosphere required.
However, alloys which contain high levels
of stable oxide formers such as aluminum,
titanium and, to a lesser extent, columbium,
will always be somewhat oxidized in spite
of good bright annealing practices. Modern
industrial equipment cannot achieve the
levels of atmospheric quality needed to
prevent oxidation of these elements.
When a truly bright-annealed surface is
required even with these alloys (brazing
for example) special techniques are used.
These include using a very thin nickel
plating (easily reduced barrier to oxidation),
pre-pickling in strong reducing acids to
deplete these elements from a thin surface
layer, and, lastly, using activated ion (deadly
fluorine gas) annealing.
There are some operational differences
between using argon or hydrogen gas.
First, hydrogen and oxygen are an explosive
mixture over a wide concentration range.
Ignition can occur very easily. Hydrogen is
thermally far more conductive than argon,
which is used as an insulating gas between
glass windowpanes. This means that

heating and cooling times are less when using hydrogen, and that
the energy consumption will be significantly higher (cuts insulating
efficiency). High velocity furnace gas should be used for fast cooling
immediately following any required soak time. This gas is typically
recirculated at high velocity through a heat exchanger to remove
heat.
Vacuum furnaces can generally achieve the best atmospheric
quality for bright annealing purposes. Vacuum levels better than
1 x 10-3 Torr should be possible in well-maintained industrial
equipment. The disadvantages of vacuum annealing are long
heating times, long soak through times (long cycle times), increased
maintenance of the equipment, and difficult cooling. Fast cooling is
generally achieved by back filling the chamber with argon or nitrogen
and then recirculating this gas at high velocity through a heat
exchanger to remove heat. Quench times should be adequate for
common 304L and 316L. Less stable alloys such as duplex 2205
or 2507 may not be compatible or may require special handling for
best corrosion resistance.
Sensitization occurs when chromium or molybdenum carbides
precipitate, typically during field welding or during service in the
temperature range of 9001500F (480814C). When this occurs,
chromium and molybdenum are no longer available to protect the
alloy in corrosive environments and the metal is sensitized.
Sensitized alloys will be more susceptible to various types of
corrosion such as intergranular SCC (stress corrosion cracking) and
pitting.
One approach for avoiding sensitizations is to lower the carbon
level as in the L grades such as 304L and 316L. This reduces the
driving force for carbide precipitation, slowing precipitation. Please
see the figure next page.

Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein.

Stabilizing Anneals

Some alloys such as 321 stainless, alloys

20 and 825 are designed to achieve
optimum sensitization resistance when
first solution annealed then followed by a
relatively low temperature stabilizing anneal.

RathGibson uses only bright annealing

in our standard production but can
perform stabilizing anneals on request.
However, for chromium-containing alloys
such as 825, a low temperature anneal
(17251800F) (940982C) will result in
a dark colored product due to formation
of some chromium oxides. Industrial
furnaces develop atmosphere dew point
(quality) levels such that temperatures
much lower than 1900F will result in some
visual chromium oxide formation. The color
obtained is a function of alloy, atmosphere
quality and temperature. If these variables
are all essentially fixed, little can be done
about the resultant color. If OD appearance
or the presence of oxide is critical for other
reasons, RathGibson can OD-polish. Our
sales group can develop cost estimates
if you have interest.

1400
Temperature

Sensitization is prevented in titanium or

columbium-containing alloys through the
use of a relatively low temperature anneal
that ties up carbon by precipitating titanium
or columbium carbides preferentially to
chromium or molybdenum. This leaves
chromium and molybdenum in solution
and available for resisting corrosive
environments. Typically, this type of
annealing is performed at 15501800F
(845-980C) depending on the specific
alloy. Because of what this low temperature
anneal accomplishes, it is more correctly
a stabilization treatment than a
solution anneal.

1600

C
900

0.080

0.062

0.056
0.058

800
0.052
700

1200

0.042

0.030
0.019%
Carbon

600
1000
500
800
10sec.

1min.

10min. 1hr.
10hrs.
100hrs. 1000hrs. 10,000hrs.
Time-Temperature-Sensitization-Curves

Time required for formation of carbide precipitation in stainless steels with various
carbon contents. Carbide precipitation forms in the areas to the right of the
various carbon-content curves. Within time periods applicable to welding,
chromium-nickel stainless steels with 0.05% carbon would be quite free from
grain boundary precipitation.

Soak times for stabilizing anneals are frequently limited for long
products such as tubing. This is simply because such long products
are typically annealed in continuous roller hearth furnaces which
have a minimum speed and cannot be fully stopped. Tubing is rolled
into the furnaces, heated to temperature and rolls out the other
end. The soak time is limited by the minimum furnace speed and
its length. Stabilizing treatments for plate are typically specified
as one hour at temperature minimum. Unfortunately, this may be
impossible in continuous furnaces.

Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein.

Stress-Relief Annealing

Magnetic Permeability

ASTM A249 Supplemental Requirement 1 (S1) specifies a

15501650F (845-900C) stress-relief anneal after roll
straightening followed by air or slow cooling. No straightening after
this anneal is permitted. This procedure is specifically for stress
corrosion cracking (SCC) environments, where residual stresses
can cause or lead to environmental cracking, particularly in alloys
such as 304L and 316L. Frequently the S1 anneal is followed by
a magnesium chloride SCC test (ASTM G36) to prove that residual
stresses have in fact been eliminated.

Austenitic stainless steels such as 304L

and 316L are nonmagnetic in the annealed,
fully austenitic condition. Welds, however,
can be mildly magnetic due to retained
weld ferrite. Cold working will also generally
increase magnetic permeability. Typical
magnetic permeability values for alloy
316L tubing are listed below.

80
Cr RANGE: 15.523%

Location

70

Base Metal
HAZ Weld

Threshold Stress Intensity (KISCC), MPa m1/2

444
904L

60

2205
304

ALLOY 718
(Solution Annealed)

317

50

ALLOY
800H
40

Contamination by any number of elements

can cause discoloration, staining, pitting
and poor corrosion resistance. Severe
irreparable damage can result from heattreating with contaminants present. Oils
or hydrocarbons often contain chloride
ions, which cause general corrosion
and pitting. Absorption of carbon can
cause sensitization and reduce corrosion
resistance in many environments.

NIMONIC
ALLOY
75

316L

30

Low magnetic permeability product can be

supplied for customers requiring these low
values. This is accomplished using extended
annealing to reduce the retained weld
ferrite.

ALLOY 600
ALLOY
800

321

A286
20
304L
10

10

20

30

40

50

60

70

80

Nickel Content (wt. %)

Effect of Nickel content on the stress corrosion cracking threshold stress of various
alloys in aerated aqueous 22% NaCl solution at 105C.
M.O. Speidel, Metallurgical Transactions A. Vol 12A, p779, 1981

Magnetic Permeability
@ 200 H (oersteds)
Mill
Extended
Anneal
Anneal
1.011.02
< 1.01
1.021.05
< 1.01
1.051.10
< 1.01

Corrosion tests exist for verifying

appropriate thermal processing for most
alloys. For most stainless alloys such
as 304L, 316L, and 317L, ASTM A262
Practices A or E are generally appropriate.
A262 addresses inter-granular corrosion
resistance in a number of different types
of environments depending on the practice
(AE), but all attempt to determine if
the material has been sensitized due to
inappropriate thermal processing.

Data shown is typical, and should not be construed as limiting or necessarily suitable for design. Actual data may vary from those shown herein.

ASTM A262 practice C (Huey test) is a 10-day test for nitric acid
service. Alloy 316L will not perform as well as 304L in this service
and, in fact, will not pass practice C consistently. For alloy 316L,
practices A or E may be more appropriate. Similarly high carbon
grades may not be compatible with practice C testing. Stabilized
grades are normally tested with practice E.
For duplex stainless steels, ASTM A923 practice A or C may be
appropriate. Depending on the service environment, other standard
corrosion tests may be appropriate.
ASTM Corrosion
Test
G28
A
B
G36

Comment
Intergranular corrosion susceptibility
Ferric Sulfate Sulfuric Acid
23% H2SO4, 1.2% HCl, 1% FeCl3+ 1% CuCl2,

Boiling 45% Magnesium Chloride for Stress Corrosion

Cracking Resistance (SCC)
Ferric Chloride (6% FeCl3) pitting test
(22 & 50C)
Ferric Chloride (6%) Crevice corrosion Test
(22 & 50C)
Ferric Chloride (6%) Critical Pitting Temperature Test

Critical Crevice Corrosion Test

A249

S7

Weld Decay

A262

Detecting Susceptibility to Intergranular

Attack Oxalic Acid Etch Screening
Detecting Susceptibility to Intergranular
Attack Ferric Sulfate (Streicher Test)
Nitric Acid (65%) (Huey Test)

G48

A
B

B
C
E

A923

Time

Alloys

Alloy
dependant
24 hr

All Alloys

Std Practice

622, 59,
686, 276
All Alloys

Std Practice

24 hr
72 hr
Standard
72 hr
Standard
72 hr
Standard

All Alloys

72 hr
Standard
1 hr*

Special
Processing

Type of Tests

Std Practice

Std Practice

All Alloys

Std Practice

All Alloys

Std Practice

All Alloys

Std Practice

304, 316,
317

None laser

Acceptance
Acceptance &
Screening
Acceptance

24 hr

Not for Mo
containing
304L,
never 316L
All Alloys

120 hr

All Alloys

Acceptance

10 days!!

304L

Acceptance

Copper Copper Sulfate Sulfuric Acid (A249 S6)

(Strauss Test)
E with 50% Sulfuric acid for castings

Sodium Hydroxide Etch Test

Duplex

Charpy Impact Test,

Requires thick wall!
Ferric Chloride Corrosion test
pH=1.3, 25C for 2205
11.9% H2SO4 + 1.3% HCI + 1% FeCl3 + 1% CuCl2

Duplex

Acceptance &
Screening
Acceptance

24 hr

Duplex

Acceptance

72 hr

High nickel
pitting alloys

Acceptance

C
Green Death*

Acceptance

* Not ASTM
For more information, please contact technical representatives at your supplier. If they are unwilling to use standard industry tests to verify
appropriate processing or service ability you could be dealing with the wrong supplier. Feel free to contact RathGibson technical personnel
at (608) 754-2222 should you have any such questions.

Data shown is typical, and should not be construed as limiting or necessarily suitable for design.
Actual data may vary from those shown herein.
The information herein was correct at the time of publication and is subject to change without notice.
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