Stress corrosion cracking and hydrogen

embrittlement cracking of welded weathering

steel and carbon steel in a simulated acid rain
environment
Y.-S. Choi and J.-G. Kim
The stress corrosion cracking (SCC) and hydrogen embrittlement cracking (HEC) characteristics of welded
weathering steel and carbon steel were investigated in aerated acid chloride solution. The electrochemical properties
of welded steels were investigated by polarisation and galvanic corrosion tests. Neither weathering steel nor carbon
steel showed passive behaviour in this acid chloride solution. The results indicated that weathering steel had better
corrosion resistance than carbon steel. Galvanic corrosion between the weldment and the base metal was not
observed in the case of weathering steel because the base metal was anodic to the weldment. However, the carbon
steel was susceptible to galvanic corrosion because the weldment acts as an anode. Slow strain rate tests (SSRT)
were conducted at a constant strain rate of 7.876107 s 1 at corrosion potential, and at potentiostatically controlled
anodic and cathodic potentials, to investigate the SCC and HEC properties in acid chloride solution. The welded
weathering steel and carbon steel were susceptible to both anodic dissolution SCC and hydrogen evolution HEC.
However, weathering steel showed less susceptibility of SCC and HEC than carbon steel at anodic potential because
of Cr and Cu compounds in the rust layer, which retarded anodic dissolution, and at cathodic potential due to the
presence of Cr, Cu, and Ni in alloy elements, which inhibit the reduction of hydrogen ions. SEM fractographs of
both steels revealed a quasicleavage fracture in the embrittled region at applied anodic and cathodic
potentials.
MST/5666
The authors are in the Department of Advanced Materials Engineering, Sung Kyun Kwan University, 300 Chunchun-Dong,
Jangan-Gu, Suwon 440 746, Korea (kimjg@skku.ac.kr). Manuscript received 9 October 2002; accepted 2 April 2003.
# 2003 IoM Communications Ltd. Published by Maney for the Institute of Materials, Minerals and Mining.

Introduction
Weathering steel has been widely used in the construction of
bridges, transmission towers, buildings, guardrails, and
lighting poles. Under suitable conditions, alloying elements
such as copper, chromium, nickel, silicon, and phosphorous
promote the formation of protective rust layers. Because of
its own protective coating, weathering steel is used outdoors
without paint or other protective coatings.1 5
Unlike painted bridges in which the steel is protected
against the environment, weathering steel bridges are
concurrently exposed to aqueous environments and subjected to vehicle-induced stress during their service life.
Before the bridge is opened to traf c and during the initial
years of service, weathering creates rust pits from which
cracks may eventually initiate. During the service life the
aqueous environment enhances crack initiation and accelerates the rate of crack propagation.6 Corrosion is the
major cause of deterioration of steel bridges. Collapses of
the Pt. Pleasant bridge over the Ohio river in 1967 and
SungSu bridge over the Han river in 1994 have been
attributed to stress corrosion cracking.7 After these
accidents, some bridges were constructed using weathering
steel to minimise the damage caused by corrosion.
However, weathering steel does not develop a protective
oxide coating under some environmental conditions. Air
pollution, prolonged time of wetness, and salt contamination have a deleterious effect on corrosion performance.
Further, applying weathering steels for use as a structural
material has been a problem because the protective
rust layer is usually formed spontaneously after 10 or
more years of exposure. Until the protective ability of the
rust layer emerges, the corrosion rate of weathering steel is
not low and initial rust contaminates other structural
materials.6
DOI 10.1179/026708303225008329

Novak8 determined the corrosion fatigue crack initiation

life of A36, A588 Grade A, and A517 Grade F steel
specimens tested in a 3.5% sodium chloride solution under
constant amplitude cyclic loading and a realistic cyclic
frequency of 12 cycles min 1 . Barsom and Novak9 published corrosion fatigue crack propagation data in the form
of plots of corrosion fatigue crack growth rate, da/dN,
versus range of stress intensity factor DK, for A36, A588
Grades A and B, and A514 steels. They were tested in air,
distilled water, and 3% sodium chloride solution. Others
also investigated the corrosion fatigue of weathering steel in
aqueous solution.1 0 ,1 1 However, little information exists on
their stress corrosion cracking (SCC) and hydrogen
embrittlement cracking (HEC) characteristics in aqueous
solutions.
The purpose of the present study was to investigate the
corrosion failure (SCC, HEC) characteristics of welded
weathering steel and to compare quantitatively the variations in SCC and HEC behaviour of welded carbon steel in
an acid chloride solution. Aqueous corrosion properties
were evaluated by potentiodynamic polarisation tests and
galvanic corrosion tests. SCC and HEC properties were
evaluated by slow strain rate tests (SSRT) over a range of
anodic and cathodic potentials. The surfaces were examined
using scanning electron microscopy (SEM) and X-ray
photoelectron spectroscopy (XPS).

Experimental procedures
MATERIALS AND CORROSIVE ENVIRONMENT
Tables 1 and 2 list the chemical compositions and mechanical properties of weathering steel and carbon steel designated as SMA 41 (JIS G3114) and SWS 400, respectively.

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1738 Choi and Kim

Cracking of welded weathering steel and carbon steel in an acid rain environment

a for electrochemical test; b for slow strain rate test

1 Schematic diagram of specimen

The weldment specimens were prepared by FCAW ( ux

cored arc welding) technique. Table 3 gives the welding
parameters and procedures.
Specimens of two different types were machined from the
welded specimens. One was of rectangular shape for
electrochemical tests, and the other was a tensile test type
for SSRT1 2 (Fig. 1). The specimens were ground with 120
grit silicon carbide paper and nished with 600 grit paper.
An aerated acid chloride solution was used to simulate an
acid rain environment (pH 6, 1000 ppm chloride). All
solutions were aerated with pure air at a ow rate of
10 cm3 min2 1 .

ELECTROCHEMICAL TESTS
Each specimen was mounted in epoxy and cured in air for
24 h. To prevent the initiation of crevice corrosion between
Table 1

Chemical compositions of base and ller metal

Composition, wt-%

SMA41

Base
Filler
SWS400 Base
Filler

Table 2

SMA41
SWS400

Table 3

Si

Mn

Cu

Cr

Ni

0.15
0.04
0.15
0.04

0. 40
0. 59
0. 35
0. 61

1 .35
1 .01
1 .35
1. 27

0.027
0.015
0.027
0.015

0.021
0.011
0.021
0.010

0.40
0.56

0.60
0.54

0.15
0.58

Mechanical properties of base and ller metal

Base
Filler
Base
Filler

Yield stress,
kg mm2 2

Tensile stress,
kg mm2 2

Elongation,
%

25
56
25
53

48
63
47
59

17
26
18
29

the epoxy and specimen, the epoxy/specimen interface was

painted with Amergoat 90 epoxy.
Electrochemical polarisation of the sample was accomplished with an EG & G Model 273A potentiostat. For each
material and electrolyte combination, the corrosion sample
was allowed to stabilise in the electrolyte. This potential was
then taken as the open circuit potential (OCP). After
immersion of the specimen in the solution for 3 h, the
potential was swept at a rate of 600 mV h2 1 . The
electrochemical test cell contained the working electrode,
a glass capillary probe connected to a reference electrode,
and two graphite rod counter electrodes. All potentials were
measured against the saturated silver/silver chloride electrode (Ag/AgCl).
A galvanic corrosion test between weldment and base
metal was made with a zero resistance ammeter (ZRA) for
72 h. Figure 2 shows the experimental arrangement. The
weldment was connected to the working electrode terminal
(anode), the base metal to the reference electrode terminal
(cathode) which were connected to the counter electrode
terminal. The ratio of weldment area to base metal area for
each specimen was 1 : 1.

SLOW STRAIN RATE TEST

The SSRTs were conducted using a CERT system with a
load capacity of 2.727 t. The tests were performed at a
constant strain rate of 7.876102 7 s2 1 . The tensile test
specimen was installed in the test cell so that the entire
gauge length of the specimen was immersed in the solution.
The test cell consisted of an acrylic vessel with two
graphite rod counter electrodes, and a reference saturated
silver/silver chloride electrode (Ag/AgCl). In the tests
at controlled potential, the specimen was polarised
either anodically or cathodically using a potentiostatic
method. Figure 3 shows the test apparatus and the
electrical connections between the test specimen and

Welding procedure speci cation*

First bead
Second bead
Third bead
Fourth bead
Fifth bead

Current, A

Voltage, V

Welding speed,
mm min2 1

Polarity

200
220
230
250
250

23
24
25
26
26

270
160
160
130
300

Direct
Direct
Direct
Direct
Direct

*Welding process ux cored arc welding (FCAW); base SMA41, SWS400; gas CO2, 15 L min2 1.

Materials Science and Technology

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current
current
current
current
current

reverse
reverse
reverse
reverse
reverse

polarity
polarity
polarity
polarity
polarity

Choi and Kim

Cracking of welded weathering steel and carbon steel in an acid rain environment

1739

Anodic polarisation curves of welded weathering steel

Results and discussion

Anodic polarisation curves of welded carbon steel

ELECTROCHEMICAL BEHAVIOUR OF THE

WELDED SPECIMEN

The corrosion current density can be measured and can

yield a corrosion rate, based on Faradays law1 3
0:13|icorr (mA cm{2 )|EM
Corrosion Rate mpy~
density (g=cm3 )
where 0.13 is the metric and time conversion factor and, EW
is the equivalent weight in grams.

2 Zero resistance ammeter for measurement of galvanic

current at short circuit

potentiostat. During the SSRTs, various mechanical

properties, such as yield stress, ultimate tensile stress,
time to fracture, elongation and reduction of area, were
measured.

SURFACE AND FAILURE ANALYSES

SEM was performed on fracture surfaces of the welded
weathering steel at different applied potentials after SSRTs.
Corrosion products on the metal surface were examined
using XPS.

Figures 4 and 5 illustrate the anodic polarisation curves of

weathering steel and carbon steel in an acid chloride
solution. Both steels exhibited active corrosion behaviour in
this solution (i.e. no passivation). This was caused by a
protective lm not forming on the surface.

3 Apparatus used for slow strain rate test

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1740 Choi and Kim

Cracking of welded weathering steel and carbon steel in an acid rain environment

6 Comparison of corrosion rate and corrosion potential

of weldment and base metal

Figure 6 shows a comparison of weathering steel and

carbon steel in terms of corrosion rate and corrosion
potential. Weathering steel had better corrosion resistance
than carbon steel.
In general, the galvanic effect accelerated the attack
between the weldment and base metal. The corrosion rate of
the metal with the more active corrosion potential, the
anode, is increased, while the corrosion rate of the one with
the more noble corrosion potential, the cathode, is
decreased. According to the polarisation curves in Fig. 4,
the base metal of weathering steel had a lower corrosion
potential than the weldment. This indicated that the base
metal acts as an anode when galvanically coupled. As
shown in Fig. 5, however, the weldment of carbon steel acts
as an anode when galvanically coupled. To evaluate the
quantitative galvanic effect between weldment and base
metal, galvanic corrosion tests were performed for 72 h
using a zero resistance ammeter.
Figure 7 shows galvanic current density versus time. The
galvanic current gives a quantitative measurement of the
capacity of the couple to generate current and indicates its
direction. Weathering steel shows a negative current value,
while carbon steel shows a positive value. The negative
galvanic current is evidence that the base metal acts as an
anode in galvanic corrosion, while the positive current means
that the weldment acts as an anode in galvanic corrosion. As a
result, the welded weathering steel was not susceptible to
galvanic corrosionbecause the base metal has larger area than
the weldment (large anode, small cathode effect). However,
the welded carbon steel was susceptible to galvanic corrosion
because of the small anode, large cathode effect.
These differences were affected by ller metal composition. It was thought that by increasing alloying elements
content, such as Cr, Cu, Ni, in weathering steel ller metal,
the corrosion potential of the weldment would increase, and

7 Galvanic current density between base metal (anode)

and weldment (cathode)

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a anodic polarisation curve; b cathodic polarisation curve of

weldment

8 Determination of applied potential

that higher Cu, Cr, and Ni content and lower C content

would provide a bene cial effect on the corrosion resistance
of the weldments.1 4

SCC AND HEC BEHAVIOUR WITH APPLIED

POTENTIALS
To determine the applied potential, polarisation tests of
the unstressed welded weathering steel and carbon steel
tensile specimens were conducted (Fig. 8). At cathodic
potentials, the possible reduction reactions are identi ed as:
I. O2 z4Hz z4ed2H2 O, II. 2Hz z2edH2 , and III.
2H2 Oz2edH2 z2(OH)2 . Only reaction I will occur at
potentials
greater
than
2950 mVA g /A g C l .
Below
2950 mVA g /A g C l , all three reactions will occur. Thus,
most of the newly formed hydrogen atoms combine to
form hydrogen molecules and harmlessly form bubbles
of hydrogen gas. However, a small percentage may enter the
material as hydrogen atoms. It is precisely these atoms of
hydrogen that can cause embrittlement of the material.1 5 1 7
As shown in Fig. 8, the anodic polarisation curves of
welded weathering steel and carbon steel are very much
alike but the cathodic polarisation behaviours are slightly
different. These results seem to indicate that the differences
in chemical composition and/or microstructure of the
weldment may affect the cathodic reaction, mainly the
reduction of hydrogen ion in acid chloride solution.
As reference information relative to the electrochemical
potentials employed in the SSRTs, anodic applied potentials were selected as 2450, 2250, 250 mVA g /A g C l and
cathodic applied potentials were 2850, 21050,
21250 mVA g /A g C l . In air and OCP tests were also conducted
to compare the effect of applied potential.
Figure 9 shows the stress strain curves of welded
weathering steel under different conditions. At OCP, the
mechanical properties during SSRT were approximately the
same as the mechanical properties measured in air. This

Choi and Kim

Cracking of welded weathering steel and carbon steel in an acid rain environment

1741

a in air and at OCP; b anodic applied potentials; c cathodic

applied potentials

9 Stress strain curves of welded weathering steel for

slow strain rate test

indicated that welded weathering steel was not susceptible

to embrittlement under natural conditions (i.e. when tested
in air or in an aqueous solution at the free corrosion
potential). When potential was applied, however, the
stress train curves showed a different behaviour. The
SSRT results for welded weathering steel at the different
potentials are given in Fig. 10.
Anodic polarisation to 2450 and 2250 mVA g /A g C l promoted general corrosion of the steel; severe embrittlement
occurred. At a more anodic potential (250 mVA g /A g C l ),
failure due to general corrosion occurred very quickly.
Increase in anodic potential caused an increase in the
number of cracks on the surfaces, which indicated increased
disturbance of the protective lm. As a result, the low
mechanical properties at the anodic applied potentials are
believed to be due to an anodic dissolution based stress
corrosion cracking mechanism.1 8
A potential of 2850 mVA g /A g C l , which is slightly
cathodic to the corrosion potential, appears to prevent
embrittlement in SSRTs. At the hydrogen producing
cathodic potentials (21050 and 21250 mVA g /A g C l ), low
percentage elongation, time to fracture, and reduction of
area values were measured indicating severe hydrogen

a tensile stress and yield stress; b time to fracture; c elongation; d reduction of area

10

Variation in mechanical properties

embrittlement. The lack of sensitivity of yield stress and

ultimate tensile stress to the failure mode can partially be
explained by the delayed cracking mechanism.1 9 It indicates
that crack initiation does not occur until after some substantial uniform elongation has occurred. In low strength
steels, enhanced hydrogen transport by plastic ow
promotes shear strain localisation and plastic instability.
This in turn can lead to either multiple slip, void nucleation
and growth, or cleavage cracking. A hydrogen embrittlement process which is activated by the presence of hydrogen
would be accelerated at more negative cathodic potentials.
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1742 Choi and Kim

Cracking of welded weathering steel and carbon steel in an acid rain environment

11 Comparison of current densities for stressed and

unstressed conditions

Figure 11 compares the current density changes as a

function of time for welded weathering steel at Ea p p ~
2250 mVA g /A g C l under stressed (SSRT) and unstressed
conditions. Initially, the current density increased with time.
Then, the current density in the unstressed condition
reached a steady state while the current density in the
stressed condition increased gradually with time. The constant stable current density value could be explained as due
to the stable corrosion product on the steel surface. When
the stress was applied, however, the process of product
repair was not as high as the rate of product rupture during
the cracking process. The current density dropped to the
minimum value when the specimen fractured.
Figure 12 shows the stress strain curves of welded
carbon steel at the various applied potentials. The welded
carbon steel was also not susceptible to embrittlement like
weathering steel at the OCP. When potentials were applied,
however, embrittlement occurred at anodic potentials where
anodic dissolution occurred and at cathodic potentials
where hydrogen was produced at the specimen surfaces.
Figure 13 compares the SSRT results of weathering steel
and carbon steel at the different potentials. In both steels,
embrittlement was greater at the anodic potential. The ductilities for the weathering steel ranged from 19% at the OCP to
13% at the cathodic potential(21050 mVA g /A g C l ) and to 9%
at the anodic potential(2250 mVA g /A g C l ). In comparison,the
ductilities for the carbon steel ranged from 20% at the OCP
to 10% at the cathodic potential (21050 mVA g /A g C l ) and to
6% at the anodic potential (2250 mVA g /A g C l ). Over the
anodic and cathodic applied potentials, weathering steel
showed more ductility than carbon steel.

12 Stress strain curves of welded carbon steel for slow

strain rate test

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a time to fracture; b elongation; c reduction of area

13

SSRT results for weathering steel and carbon steel

14

Comparison of current densities for WS and CS at

250 mVAg /AgCl

Choi and Kim

Cracking of welded weathering steel and carbon steel in an acid rain environment

16

15

XPS spectra of weathering steel and carbon steel

obtained from rusting surfaces

1743

Hardness distribution of weathering steel weldment

Figure 14 compares the anodic current density as a

function of time at Ea p p ~2250 mVA g /A g C l under the SSRT
condition. The increased current appears to be the result of
the increased anodic kinetics. During the SSRTs, corrosion
current densities of carbon steel became higher than those
of weathering steel. It was thought that, based on this result,
a more stable rust layer was developed on the weathering
steel surface because of its alloying elements. These alloying
elements, such as chromium, copper, and nickel, promote
formation of a more stable rust layer on weathering steel.
As mentioned above, the difference between the SCC
resistance in weathering steel and carbon steel was related to
the rust layer. Thus, it is necessary to examine the rust
constituents in an aqueous condition for their corrosion
resistance. XPS spectra of steels obtained from rusting
surfaces after SSRTs are shown in Fig. 15. There was some
chromium oxide (Cr2 O3 ) and cupric oxide (CuO) in the rust
layer of the weathering steel. It was known that the
corrosion resistance of weathering steel is similar to that of
carbon steel in the aqueous solution.2 0 As mentioned in
previous work,2 1 however, the alloying elements, such as
chromium and copper, formed compounds or oxides and
these compounds promote more or less protective rust
layers on weathering steel in an aqueous condition, than
they do with an atmospheric condition. It seems reasonable
to assume that this is good evidence for the greater
resistance to SCC of weathering steel than for carbon steel.

b
a SMA41: air and OCP; b SWS400: air and OCP

17

Macrographs of welded weathering steel and carbon steel fractures in air and at OCP

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1744 Choi and Kim

Cracking of welded weathering steel and carbon steel in an acid rain environment

b
a SMA41; b SWS400

18 Fractographs of welded weathering steel and carbon steel fractures from anodic applied potential test

The superior HEC resistance of weathering steel is

explained as follows. As shown in the polarisation curves
in Fig. 8b, the variation in cathodic characteristics between
the weathering steel and carbon steel may partly explain the
local anodic/cathodic behaviour of a steel weldment.1 4 Thus,
the presence of Cu, Cr, and Ni in weathering steel seems to
inhibit the reduction of hydrogen ion in acid chloride solution,
which in turn causes a decrease in HEC susceptibility.

FAILURE ANALYSIS
Regardless of the testing environment and material,
fractures in both welded weathering steel and carbon steel
were located at the base metal, which had the lowest
hardness compared to other parts of the weld (Fig. 16).
Figure 17 shows the fracture surfaces of weathering steel
and carbon steel, tested in air and at the OCP. In these
environments, a completely ductile cup and cone fracture
mode was observed.
Low and high magni cation views of the welded weathering steel and carbon steel, tested at 2250 mVA g /A g C l and

at 21050 mVA g/A g C l are shown in Figs. 18 and 19. Both steels
exhibited transgranular cleavage like fracture surfaces, and
secondary cracks were observed near the main fracture. The
transition from brittle, transgranular propagation in the SCC
and HEC region to ductile, dimpled propagation in the
mechanical region is apparent. Ductile fracture was observed
near the centres of the specimens, where the remaining
ligaments failed by ductile overload once cracking initiation
reduced the cross-section of the specimens.
Thus, these surface observations support the conclusion
that the susceptibility of corrosion failures in welded
weathering steel and carbon steel is predominantly determined by the electrochemical reaction.

Conclusions
1. Welded weathering steel and carbon steel did not show
passive behaviour in acid chloride solutions; they exhibited
active corrosion in this environment.

b
a SMA41; b SWS400

19 Fractographs of welded weathering steel and carbon steel from cathodic applied potential test

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Choi and Kim

Cracking of welded weathering steel and carbon steel in an acid rain environment

2. Welded weathering steel was not susceptible to

galvanic corrosion because the base metal was anodic to
the weld metal (large anode, small cathode). However, the
welded carbon steel was susceptible to galvanic corrosion
because of the small anode, large cathode effect.
3. Both steels investigated were not only susceptible to
anodic dissolution SCC but also to hydrogen evolution
HEC. However, the mechanical properties of the welded
weathering steel were signi cantly better than those of the
carbon steel.
4. Weathering steel shows less susceptibility to SCC and
HEC compared to carbon steel at applied anodic potentials
because of the chromium and copper compounds in the
rust layer, and at cathodic potentials due to the presence of
Cr, Cu, and Ni in alloy elements, which inhibit the
reduction of hydrogen ions. These alloying elements
improve the SCC and HEC resistance of weathering steel
in aqueous environments.

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steel in bridges, Report 272, National Cooperative Highway
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6. p. albrecht: in Corrosion forms and control for infrastructure, STP 1137, 108; 1992, Philadelphia, PA, ASTM.
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