Improvement of Corrosion-Erosion Resistance of Martensitic Stainless Steels by Nitrogen

Addition at High Temperature

A. Toroa, D. K. Tanakab, A. Sinatorab, A. P. Tschiptschina

aMetallurgical and Materials Engineering Department – University of Silo Paulo

bA4echanical Engineering Department – Universi~ ofSi70 Paulo
Av. Pro$ IWlo Moraes 2463, CEP 05508-900, Siio Paulo / Brazil

Abstract

AISI 410S (13%Cr-O.08%C max.) stainless steel specimens were nitrided at 1473 K under 0.25
MPahigh purity nitrogen atmosphere, andthen oilquenched andtemperedat473K. After this
treatment, 2 mm-depth martensitic cases with 0,52 wt% N at the surface were obtained, the
nitrogen content at the core being 0.035 wt%. Slurry wear tests were performed by placing the
specimens in a stainless steel vessel containing substitute ocean water (ASTM D1 141 Standard)
and quartz particles with 0.3-0.5 mm diameter. The particle impact velocity, pll of solution, impact
angles and solid content of the slurry were controlled. The slurry temperature, mass losses, surface
damages and microstructure changes were periodically monitored during the 96 hours tests.
Quenched and tempered AISI 410 and AISI 420 stainless steels were used as comparison materials.

The erosion-corrosion resistance of the nitrided and 473 K tempered AISI 410S steel was better
than that of the AISI 410 and AISI 420 steels. This behavior was primarily due to the better
corrosion resistance of the nitrided alloy, measured by potentiodynamic method. Scanning Electron
Microscopy showed that intergranular corrosion of the AISI 410 and AISI 420 alloys was an
important cause of mass loss, while it was not observed in the nitrided specimens.

Keywords: Nitrogen addition to steels; Corrosion-erosion resistance; Slurry wear

1. Introduction

A wide variety of techniques including alloying, coating deposition and thermo-chemical treating
have been used to improve stainless steels’ corrosion-wear resistance. Guenbour et all studied the
influence of alloying elements in corrcwion-abrasion of stainless steels in phosphoric acids
containing chloride ions and SiC particles. Hodgkiess et a12 used a cerrnet coating material
thermally sprayed onto stainless steel discs to enhance the resistance to corrosion-erosion in saline
solution with silica particles. Berns et a13 improved the corrosion resistance of near net shape
components for petrochemical industry by nitrogen addition in solid state. Synergism between
corrosion and wear is extremely important for a wide range of applications regarding the use of
stainless steels.

It has been established that nitrogen improves the pitting corrosion resistance of stainless steels475’G,
although the chemical andhr electrochemical mechanisms that explain this effect are not clearly
established. Conversely, experimental results concerning the effect of nitrogen alloying on
generalized corrosion resistance are, in many cases, contradictoryGy7.The beneficial effect of
nitrogen on erosion resistance is commonly associated to solid solution hardening and second
phase precipitation; hard chromium nitrides and carbonitrides provide good abrasion wear
resistance, but in some cases the corrosion resistance is seriously reduced due to chromium
depletion of metallic matrix8>9.

Three main routes are commonly used for obtaining high nitrogen steels: high-pressure meltinglO,
powder metallurgy* and solid-state alloying*2. Melting under pressure is recommended for large-
scale fabrication but it rec~uirescomplex and costly equipment; powder metallurgy requires a hot
isostatic pressing stage to obtain full-density components. Solid-state alloying allows changing the
surface properties of several materials with minor modification of bulk properties. When dealing
with wear and corrosion, solid state alloying is one of the most suitable processes due to reduced
costs and simplicity.

The aim of this work is to study the effect of nitrogen solid state alloying on the corrosion-erosion
resistance of a martensitic stainless steel tested in seawater-quartz slurry.

2. Experimental Procedure

The chemical composition of the stainless steels used in this investigation is shown in Table 1.

Table 1. Chemical composition (wt.!!40) of AISI 410S, 410 and 420 stainless steels.

— Steel Cr c Ni Mn Si N
AISI410s 13,0 0,07 0.20 0.38 0.36 0.035
AISI41O 11.5 0,13 0.20 0.60 0,36 0.015
_ AISI 420 12,4 0.37 0,75 1,00 0.24 0.018

2.1. High temperature nitriding of AISI 410S steel and heat treatments

AN 410S steel was gas nitrided in an experimental setup described in a previous work13. The
specimens were placed in a tubular furnace and heated up to 1,473 K under 10-3Torr vacuum
during 1 hour. High purity nitrogen was introduced in the fwace and the system was maintained at
0.25 MPa during 6 hours. At the end of the treatment the specimens were oil quenched and
temperecl at 473 K during 1 hour under 0.15 MPa argon atmosphere. AISI 410 and AISI 420 steels
were austenitized at 1,273 K during 1 hour under argon atmosphere, oil quenched and tempered at
the same conditions used for the nitrided AISI 410S specimens. After the treatments, all the
specimens were polished to 0.03*0.02 pm to standardize the surface finishing conditions for
corrosion-erosion tests.

2.2. Corrosion – Erosion tests

Corrosion-erosion experiments were performed in the test machine shown in Figure 1. It consists
of a stainless steel vessel containing slurry made of substitute ocean water and 20°/0quartz particles
(0.3-0.5 mm diameter). The specimens were fixed to electrically insulated metallic holders. The
setup allowed the adjustment of impact angles to 45° or 90°. The slurry was impinged against the
specimens’ surface by a polypropylene disk driven by an electronically controlled electric motor.
The temperature of the slurry, as well as specimens’ mass losses and roughness changes were
periodically measured. The slurry was renewed after every 96 hours test cycle. Specific mass loss
~, defined as the quotient betweem the Cumulative mass loss AW (in gram) and the geometrical
exposed surface S (in m2) was used to normalize the mass loss results.
 ‘“”””
fii&2
Fmmncy
amewor

II
!
E
E
.,. . :
,/ .””””,
W. . . .
\ ?~ . .
?5
:

%-
emm
a b
Figure 11. a) Schematic of slurry wear testing machine; b) Shape and dimensions of the test
sp~cimens; e) Morphology of qua% particles us~d in erosion and corrosion-erosion testing (SEM).

In order to study the synergism between corrosion and wear, non-corrosive erosion tests were
carried out replacing substitute ocean water by tap water, while solids-free impingement tests were
petiormed in solids-free substitute ocean water.

2.3. Evaluation methods

The nitrogen contents in the gas nitrided specimens were analyzed by Fusion Under Inert Gas and
Glow Discharge Optical Spectrometry (GD-OS) techniques. Changes in surface finishing were
analyzed with Scanning E1ectron Microscope and stylus profile roughness tester. Mass losses were
measured with a precision analytical scale with 0.1 mg sensitivity.

3.Results and discussion

3.1. Specific mass loss

Figure 2 shows the typica’1variation of specific mass loss as a function of the testing time for AISI
410/420 and nitrided AISI 410S steels. Figure 3 shows the effect of synergism between corrosion
and wear for AISI 420 and nitrided AISI 4 10S specimens, calculated from the specific mass losses
obtained after 96 hours tests. The nitrided AM 410S specimens showed the better resistance to
corrosion-erosion, both under 45° and 90° impingement angle, when compared to those of AISI
410/420.
350 , I
300-
250-
200-
150-
100-
50-
0
0 20 40 60 80 100
Time(hours)
--D- Nit. AH 410S,90° ~Alsi 410,90°
-~Alll 420,90° -. H .- Nit. AISI 410S, 45”
--+ -ml 410,45” -- -Q--- AH 420,45°

Figure 2. Variation of specific mass loss of specimens as a fi.mctionof testing time.

Under oblique incidence cutting would be the dominant wear mechanism; the better resistance of
the nitrided steel under these conditions can be associated to its high hardness. Under normal
incidence, martensite brittle fracture and spalling of second phase particles are expected; the
absence of coarse precipitates in the nitrided AISI 410S prevents its spalling.
Wwllml
6W
.,”.. . .—- -.. ,,
/--

410s-90° 410s-45° 420-90° 420-45”

llJErosion x Corrosion ❑ 4Erosion-CorrosionfFISweraism I
Nltrkkd AISI 4 f OS ’30a 78%

Figure 3. Synergism between erosion and corrosion in AISI 420 and nitridedAISI410S steels.

Synergism between corrosion and wear was greater in the AISI 420 specimens than in the nitrided
ones. This result can be associated to the better corrosion resistance of thenitridedAISI410S steel
in saline environments, which was confirmed by electrochemical tests accomplished in 0.5M
H2S04 + 3.5%NaCl solution.

3.2. Effect of microstructure and chemical composition

Figure 4, shows the measured and calculated14 nitrogen profiles for the AISI 410S steel after gas
nitriding at 1,473 K under 0.25 MPa NZatmosphere. The nitrogen content at the surface was 0.52°/0
before and 0.45?40after final polishing, due to material removal from the surface. The nitrogen-
enriched case was composed by a martensitic region with 1.1 mm thick, followed by a duplex
ferrite/martensite region with ca 1 mm. No precipitates were detected by SEM analysis (Figure 5)
allowing the assumption that all nitrogen is in solid solution in martensite and ferrite. This is
supported by Thermocalc@ simulation, which showed that the N2 e 2~]Y reaction is the only one
occurring at 1,473 K under 0.25 MPa Nq pressure15.All the nitride-forming reactions are inhibited
at these conditions. Figure 6 shows a calculated phase diagram illustrating several solid-gas
equilibrium conditions as a function of nitriding temperature under 0.25 MPa N2 pressure.

O Pkmhmhess

❑tv16fSurdml
ACdwk$d %$4

0 0,2 0,4 0,60,8 1 1,2 1,4 1,6 1,8 2 2,2

Diatmce to SUrfaoa(mm)

Figure 4. Micro-hardness and measured and calculated nitrogen profiles of gas nitrided AISI 410S
stainless steel. Nitriding conditions: 1473 K, 0.25 MPa Nz pressure, oil quench.
The microstructure of quenched and tempered AISI 410/420 stainless steels was composed by
martensite with precipitated carbides, which were localized p~deferentially at prior austenite grain
boundaries.

a) b) c)
Figure 5. Microstructure of martensitic case (a) and duplex martensite/ferrite region (b) of nitrided
and tempered AISI 4 10S; and c) microstructure of quenched and tempered AISI 420.
1!3W3 ‘~ , , , , ,

T (K)
Twccr
150t3 - I

m C*
1450-

i390 -

12012 -

liwa-
,r i Gl,w

iaOO
1’0 l’5 A A ?0 3’5 40
A w ““

Figure 6. Calculated phase diagram for Fe-13%C~-\ alloys in equilibrium with gaseous nitrogen at
0.25 MPa pressure. Some experimental results obtained after 6 hours-nitriding are shown.

The higher corrosion resistance of nitrided AISI 410S specimens can be attributed to a high
nitrogen content in solid solution, leading to a lower chromium depletion in the matrix after 473 K
tempering. It is known that these two characteristics promote the increase in pitting and
intergranular corrosion resistance of stainless steels5>G,and the results of this work suggest that a
reduction in synergistic effects could also be expected.

3.3. Effect of impingement velocity

Ntrided and Terrpered AISI 410s Quenched and Teqwed A161420

~25, 250 I
E y = 1,469~x2,’554 “=

y = 8,6863x251f
520- ■ E 1?= 0,961 ~ 200-
f R2 = o,9959
*E
~15- ❑ C-E J 150 -
G C-E
/ ; 100-
=1:: #’J&;::;, 4 50-
&
%.
o ~—1 0 , I ——
1 1,5 2 2,5 3 3,5 4 1 1,5 2 2,5 3 3,5 4
Impact Vellocity (m/s) Inpact Velocity (m’s)

Figure 7. Effect of impact velocity on specific mass loss under erosion and corrosion-erosion of
the AISI 420 andnitridedAISI410S steels. Substitute Ocean Water + 20% quartz particles.
Figure ‘7 shows the variation of specific mass loss @ of AISI 420 and nitrided AISI 410S
specimens as a function of impingement velocity V, under corrosion and corrosion-erosion
conditions. The accepted relationship8y1G@ = k V n (where k and n are constant) is observed,
being the velocity exponent n greater when corrosion is present. The increase in the value of n, due
to corrosion, is more accentuated in the carbon-alloyed than in the nitrided steels, which indicates a
better resistance of the nitrogen bearing alloy to the synergistic effects discussed above.

4.Conclusions

4.1. Nitrided, direct quenched and 473 K tempered AM 410S steel was more resistant to
corrosion-erosion than AM 410 and AISI 420 quenched and tempered at the same temperature,
when tested in a slurry composed by quartz particles in substitute ocean water.

4.2. The synergistic effects between corrosion and erosion mechanisms were more accentuated in
AISI 410/420 stainless steels than in the nitrided AISI 410S. Better intergranular corrosion and
reduced spalling of second phase particles of the nitrided low carbon martensitic stainless steel
strongly contribute to this performance.

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