UCRL-TR-203711

L AW R E N C E
LIVERMORE
The Cleaning of 303
N AT I O N A L
LABORATORY Stainless Steel

T. H. Shen

April 22, 2004

THIS DOCUMENT WAS PREPARED AS AN ACCOUNT OF WORK SPONSORED BY AN AGENCY OF
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THIS WORK WAS PERFORMED UNDER THE AUSPICES OF THE U.S. DEPARTMENT OF ENERGY
BY UNIVERSITY OF CALIFORNIA, LAWRENCE LIVERMORE NATIONAL
LABORATORY UNDER CONTRACT W-7405-ENG-48.

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 THE CLEANING OF 303 STAINLESS STEEL

Tien H. Shen

Materials Science and Technology Division

Chemistry & Materials Science Directorate

ABSTRACT

The sulfur found on the surfaces of stainless steel 303 (SS303) after
nitric acid passivation originated from the MnS inclusions in the steel.
The nitric acid attacked and dissolved these MnS inclusions, and re-
deposited micron-sized elemental sulfur particles back to the surface.
To develop an alternative passivation procedure for SS303, citric and
phosphoric acids have been evaluated. The experimental results show
neither acid causes a significant amount of sulfur deposit. Thus, these
two acids can be used as alternatives to nitric acid passivation for NIF
applications. For SS303 previously passivated by nitric acid, NaOH
soak can be used as a remedial cleaning process to effectively remove
the sulfur deposits.

************************************

INTRODUCTION

In November 2001, the kinematic mounts made from 303 stainless steel (SS303) showed
a high level of non-volatile residue (NVR) after nitric acid passivation followed by
precision cleaning. The NVR, identified by John Ertel using Gas Chromatography/Mass
Spectrometry (GC/MS), contained a high level of sulfur. Since sulfur is not permitted in
the NIF laser beam environment, where equipment or parts (such as reflectors) may be
silver coated, the presence of sulfur on the surface of SS303 components is a concern.

This investigation was initiated 1) to study the origin of sulfur on the surface of SS303
after nitric acid passivation, 2) to develop an alternative passivation and cleaning
procedure and 3) to develop remedial cleaning procedure for SS303 parts that previously
received the nitric acid passivation.

THE ORIGIN OF SULFUR

The 303 stainless steel (sometime referred to as “free-machining” stainless steel) has
chemical composition sim ilar to that of SS304 except that sulfur is intentionally added to

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form MnS inclusions in the microstructure. Table I shows the nominal chemical
composition of these two alloys.

Table I The nominal chemical composition of stainless steels 303 and 304.

Type C Mn Si Cr Ni P S
SS303 0.15 2.00 1.00 17.0-19.0 8.0-10.0 0.2 0.15 min.
SS304 0.08 2.00 1.00 18.0-20.0 8.0-10.5 0.045 0.03

Figure 1 shows a typical microstructure of SS303. The MnS stringers help to promote
the easy breakup of metal chips during machining.

It is likely that the sulfur found in the NVR measurements originated from the metal
itself. To identify the origin of sulfur, an experiment was performed to simulate the hour-
long nitric acid passivation followed by a precision cleaning with a mirror-polished
SS303 sample. Figure 2a shows that the 35 vol%† nitric acid dissolved the MnS
inclusions and left many pits behind. Micron-sized elemental sulfur particles, which
were identified by EDXS/SEM as shown in Figure 2b, were re-deposited back to the
surface in the vicinity of these pits as indicated by arrows in Figure 2a. Apparently, the
precision cleaning could not remove these sulfur particles.

A thermodynamic calculation1 suggested that MnS was thermodynamically unstable

above a potential of 100mV‡ and could not exist in solution with pH less than 4.3. The
strong oxidation potential of the nitric acid could dissolve the MnS and redeposit sulfur
according to the reactions 1, 2, 3:

MnS + 2H+ Mn2+ + H2S [1]

H2S S + 2H+ + 2e- [2]

The observation of the elemental sulfur particles is consistent with these reactions.

The precision cleaning that followed the nitric acid passivation could not remove these
sulfur deposits from the surface as shown in Figure 2b. Thus, it is likely that the sulfur
found in the NVR measurements was generated by the nitric acid during the passivation
process.

EXPERIMENTAL PROCEDURES

To confirm this preliminary finding and develop an alternative to the nitric acid
passivation, phosphoric and citric acids have been evaluated in this investigation.
Furthermore, since some sulfur was apparently rinsed off by the FreonTM during the NVR
measurements, this experiment also evaluated the effectiveness of using solvent to
remove sulfur from the surface after the acid passivation.
†
The 35 vol% concentration is derived by diluting 50% of a 70 vol.% reagent grade nitric acid.
‡
Against Standard Hydrogen Electrode.

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Three 12"x12" SS303 plates with machined surface (roughness (ra) 32 µinch) were
used for this experiment. These plates were machined using NIF approved cutting fluid.
The two sides of each plate were identified as A and B.
The experimental procedures are outlined as follows:
1. Each plate was high pressure detergent washed with 5% Brulin 1990 GD
solution, and rinsed with high pressure spray of process water§.
2. First NVR measurement was taken from Side A of each plate.
3. Each panel was treated with different acids as indicated below:
Plate 1): 50 vol% nitric acid, 60 min.,
Plate 2): 15 vol% citric acid gel, 120 min.,
Plate 3): 15 vol% phosphoric acid gel, 90 min.
4. After the passivation, each plate was rinsed with high-pressure spray of
process water.
5. A final wash of each plate with 5% Brulin solution, and rinsed with high
pressure spray of process water.
6. Second NVR and the first particle swipe were taken from Side A of each
plate.
7. Soaked the test panels in acetone** for 10 min., followed by hand-wiping of
each plate with acetone.
8. The third NVR was taken followed by particle swipe from Sides A and B,
respectively, of each plate.

RESULTS

Table II shows the results of the experiment. This experiment again confirms the
preliminary finding that the nitric acid passivation of SS303 (Plate 1) caused high NVR
and high particle swipe values.

Table II The results of nitric, citric and phosphoric acid passivations on

NVR and particle swipe.

Results of NVR (µg/cm2) / Particle Swipe

Plate 1 Plate 2 Plate 3
Cleaning and Nitric (60 min.) Citric (120 min.) Phosphoric (90 min.)
Passivation Steps Side A Side B Side A Side B Side A Side B
After 1st Brulin Wash 0.52 / - - 0.46 / - - 0.49 / - -
Acid Passivation - - - - - -
After 2nd Brulin Wash 0.11 / 66 - 0.01 / 69 - 0.08 / 74 -
Acetone Soak & Wipe 0.05 / 92 0.14 / 86 0.04 / 66 0.02 / 75 0.02 / 81 0.03 / 74

§
The process water was pressurized to 2,500 psi and heated to 43-54°C. This condition applied to all
the remaining procedures.
**
We choose acetone since John Ertel had shown that the acetone could reduce sulfur of a 303 plate that
failed previously of NVR.

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Both citric acid and phosphoric acid passivations reduced the NVR and particle swipe to
an acceptable level of less than 0.1 µg/cm2 and level 83, respectively. Figure 3 shows
the surface morphology of the SS303 after the citric acid and phosphoric acid
passivations. Both acids attacked the MnS inclusions and left pits behind. However, the
SEM investigation did not find any sulfur particles in the vicinity of these pits.

The acetone soak after the nitric-acid passivation was not consistently effective in
removing the sulfur from the surface. Subsequently, several solvents, i.e. FreonTM,
isopropyl alcohol (IPA) and hot D.I. water, had also been evaluated for their effectiveness
in removing the sulfur. However, the experiments showed erratic and inconsistent NVR
results. Figure 4 shows that the hot D.I. water didn’t noticeably dissolve the sulfur
particles, but Freon did show some effectiveness in dissolving the sulfur particles.
However, sulfur particles were still present after several Freon rinses.

DISCUSSIONS

In general, the primary purpose of passivation of stainless steel is to enhance its corrosion
resistance and prevent the “rouging” 4 from occurring. In cleaning NIF parts, the
passivation serves as part of the cleaning procedure to ensure the surfaces of stainless
steel from contaminants, such as metal fines, welding debris, before the precision
cleaning. In the case of SS303, the generation of sulfur during nitric acid passivation
presents an additional problem. This study has shown that by replacing the nitric acid
with citric or phosphoric acids during passivation, the problem of surface sulfur deposits
can be effectively mitigated. However, the author cautions the reader that the citric and
phosphoric acids are not effective passivation methods for SS303 for application in
aggressive corrosion environment, such as salt containing atmosphere. This study has
conducted a very extensive corrosion test in a salt spray environment on SS303 and
SS304 passivated either by nitric, citric or phosphoric acids. These test showed that the
citric acid passivated SS303 has poor corrosion performance compared to that of the
nitric acid passivated SS303. However, from the corrosion point of view, the atmosphere
inside the NIF beam line is rather benign and aggressive corrosion is not a concern. For
the briefness of this report, these corrosion results are not presented and discussed here.

Remedial Cleaning Procedure For SS303 parts that previously received the nitric acid
passivation, the experimental results show that solvents and hot D.I. water were not
effective in removing the element sulfur. Hence, an alternate approach to removing
sulfur was necessary.

It has been shown that the nitric acid is not effective in passivating free-machining
stainless steels 5. To properly passivate SS303, a NaOH soak after an nitric acid
passivation is necessary to improve the corrosion resistance in a salt spray environment.
It was suggested 5 that residual nitric acid might be retained inside the pits after the
passivation and degraded the corrosion resistance. The NaOH soak neutralized the
retained nitric acid thus improving the corrosion resistance of SS303. To verify the
effectiveness of NaOH soak, several experiments have been conducted to evaluate the

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corrosion performance of SS303 treated by 5 vol% NaOH at 70°C for 30 minutes after
the nitric acid passivation. The results showed that the corrosion performance was indeed
improved with the NaOH soak. Figure 5 shows that the NaOH dissolved the sulfur
particles, as indicated by arrows, and improved the pitting corrosion resistance of SS303
after the nitric acid passivation.

To pursue the NaOH soak as the remedial cleaning method for nitric-acid passivated
SS303, a precision cleaning experiment was conducted on two 12” x 12” SS303 panels as
follows:

1. Detergent-washed both panels with a high pressure (2,500 psi) solution

containing 5% Brulin 1990 GD, heated to 43-54°C and rinse with high
pressure spray of process water heated to 43-54°C.

2. Passivated the two panels with 50 % nitric acid for 60 min with Side A up
follow by DI water rinse.

3. Soaked Panel 2 in 5% NaOH at 70°C for 30 min. with Side A up, follow by DI
rinse.

4. Detergent-washed both plates with a high pressure (2,500 psi) solution containing
5% Brulin 1990 GD, heated to 43-54°C and rinsed with high pressure spray of
process water heated to 43-54°C.

5. Took NVR followed by particle swiping from Side A of each plate.

Table III shows the result of this cleaning experiment. The NaOH soak generated other
type of compounds (not yet identified) on the surfaces of the sample and failed the NVR
and particles swipe. However, the cleanliness can be improved by hand-wiping the
NaOH treated SS303 with 100%IPA.

Table III The result of NaOH soak cleaning experiment.

Particle Swipe NVR (mg/ft2)

Panel 1 (Nitric passivated) 71 0.13
Panel 2 (Nitric passivated + NaOH Soak) 90 0.14
After hand-wipe with IPA 65 0.02

Based on this result, we recommend the use of NaOH soak followed by wiping with
100% IPA as the remedial cleaning procedure for SS303 parts that previously received
the nitric acid passivation. However, for intricate parts which have surfaces that could
not be easily reached by hand-wiping. The use of SS303 with nitric acid passivation
followed by NaOH soak is not recommended.

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 CONCLUSION

• The sulfur found on the surfaces of SS303 after the nitric acid passivation originated
from the MnS inclusions in the steel. The nitric acid attacked and dissolved these
MnS inclusions. Elemental sulfur was re-deposited back to the surface as either
sulfur film or micron-sized particles. In addition, the pits left behind by the MnS
inclusions were also filled with a high concentration of sulfur.

• Neither citric-acid nor phosphoric-acid passivation result in significant sulfur deposits

after passivation. Thus, these two acids can be used as an alternative acid to passivate
SS303.

• The NaOH soak after the acid passivation removes the sulfur deposits and
significantly improves the pitting resistance of the acid-passivated SS303, but
surfaces must be wiped with 100% IPA to meet NIF cleanliness requirements. Thus,
we recommend the use of NaOH soak followed by wiping with 100% IPA as the
remedial cleaning procedure for SS303 parts that previously received the nitric acid
passivation.

ACKNOWLEDGEMENTS

The author would like to express his thanks to Ed Lindsey for conducting the SEM-
EDXS analysis. As always, the encouragements and suggestions offered by Bill Gourdin
during the course of this investigation and the reviewing of this manuscript are also
greatly appreciated.

REFERENCES

1. G. Eklund, “Initiation of pitting at sulfide inclusions in stainless steel”, J.

Electrochem. Soc 121(1974), pp461- 413.
2. G. Wranglén, “Pitting and sulphide inclusions in steel”, Corrosion Sci. 14 (1974) pp
331-349.
3. J. Stewart and D. Williams, “ The initiation of pitting corrosion on austenic stainless
steel: on the role and importance of sulphide inclusions”, Corrosion Sci. 33 (1992)
pp 457-474.
4. R. Coreett, “Rouging – A discoloration of stainless steel surfaces”, Materials
Performance, Vol. 40 (2001), No. 2, pp 64- 66.
5. T. DeBold, “Passivating Stainless-Steel Parts”, Machine and Tool Blue Book, vol. 81
(Nov. 1986), pp 74-77.

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 As-Polished Condition

Figure 1 Typical microstructure of 303 stainless steel. The long stringers are
MnS inclusions.

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Figure 2a shows that the nitric acid dissolved the MnS inclusions and left many pits behind.
Micron-size elemental sulfur particles, identified by EDXS as shown in Figure 2b, were re-
deposited back to the surface in the vicinity of these pits as indicated in Figure 2a. The
precision cleaning that followed the nitric-acid passivation could not remove these particles.

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Figure 3 Both citric and phosphoric acids attacked the MnS inclusions and left pits behind.
However, no elemental sulfur deposits were found in the vicinity of these pits.

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After 50 vol% nitric acid
passivation for 60 min.

After 50 vol% nitric acid

passivation for 60 min.

Hot D.I. Water at 150°F

for 10 min.

After 50 vol% nitric acid

passivation for 60 min.

Hot D.I. Water at 150°F

for 10 min.

Freon rinse

Figure 4 The sulfur particles, as indicated by arrows, didn't significantly dissolve by the hot
DI water. However, Freon shows some capability in dissolving the sulfur.

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After nitric acid
passivation

Nitric acid
passivation
+
NaOH
Neutralization

Figure 5 The NaOH dissolved the sulfur particles, as indicated by arrows, and improved the
pitting corrosion resistance of SS303 after the nitric-acid passivation.

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