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1996
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0010-938X(96)00109-3
Institute of Materials Engineering, National Taiwan Ocean University, Keelung, Taiwan 20224
Abstract-An electrochemical permeation technique was performed on mild steel and S45C medium carbon steel.
Mild steel shows higher permeation rate and diffusivity than medium carbon steel. The highest permeability and
diffusivity for heat treated medium carbon steels are observed in the spheroidized condition and least permeability
and diffusivity are in the martensitic condition. Annealed and normalized structures yield intermediate values of
permeation rate and diffusivity. A monolayer of AgBr emulsion was coated on the determination site of a specimen
to observe hydrogen transport in carbon steel. This hydrogen microprint technique also confirms that the main
diffusion path is lattice and carbide/ferrite interfaces in pearlitic and spheroidized steels, and lath interfaces in
martensitic steel.
Ke~~ds: A. steel, B. hydrogen permeation.
INTRODUCTION
Gas phase and electrochemical permeation measurements show that hydrogen diffusivity in
carbon steels is inversely dependent upon carbide volume fraction and directly dependent
upon iron carbide fineness as established by heat treatment. Hydrogen permeability is also
inversely dependent upon carbide volume fraction but shows only slight inverse dependence
upon iron carbide fineness. ‘-’ Pressouyre’ recently introduced the concept of obstacles and
repellers and related this concept to hydrogen diffusion, solubility and embrittlement. One
reasonable possibility is that carbides act as obstacles or repellers to the diffusion of
hydrogen; another suggests that fine coherent carbides act as reversible traps.’ Since the
former explanation depends upon carbide spacing or mean free path and the latter depends
upon carbide size or surface area, direct observation techniques which detect the hydrogen
distribution in carbon steel would be expected to correlate with permeation data.
The purpose of this study is to develop a better understanding of hydrogen transport in
two phase iron-carbon steels. The application of a hydrogen microprint technique to study
hydrogen distribution in carbon steels has been developed recently,‘03” and is proving to be
very simple and accurate compared with autoradiography. A hydrogen microprint
technique was used to observe the hydrogen distribution which would be expected to
correlate with permeation data and diffusion path.
DATA ANALYSIS
Permeation
For this study, the flux of hydrogen through the specimen (molHm-2 s-l) was
239
240 W. C. Luu and J. K Wu
measured in terms of current density i,, and conversion to hydrogen permeation flux
according to the following equation:
J, = iF/rrF. (1)
For effective diffusion, the rate limiting step Deff (m’ s- ‘) is related to time lag by’*
Deff = L’/6tL. (3)
where lL is lag time and Deb is determined from the transient, tL.
EXPERIMENTAL METHOD
Electrochemical permeation
The instrumentation and procedures were similar to those described elsewhere.‘j The
cathodic side, or hydrogen entry side, of the cell was galvanostatically polarized at a
constant charging current density (10 mA cm-‘) in 0.1 N NaOH with 1.0 gl-’ of
Na2S.9H20 added as a hydrogen recombination poison. The anodic side, or hydrogen
exit side, of the cell was held at a constant potential of + 250 mV (SCE) in 0.1 N NaOH at
room temperature. The potentiostatic current gave a direct measure of the hydrogen flow
rate. Solutions on both sides of the membrane were de-oxygenated. Permeation transients
were recorded on a strip chart recorder. Preliminary experiments indicated good
reproducibility after an initial charging run was made on each sample. Similar
observations reported by Xie and Hirth are thought to result from the initial filling of
deep traps.’
The test materials were commercial mild steel and S45C medium carbon steel; chemical
analyses are shown in Table 1. Preparation of these specimens (3.0-3.6 cm diameter disc,
Steel C Si Mn S P Fe
Table 2. Permeation rate and diffusivity for tested materials with a constant charging current
density (IOmAcm-*) at 25°C
annealed condition can be seen to have higher permeation rate and diffusivity than annealed
S45C medium carbon steel at a constant charging current density (10 mA cm-‘). Both J, L
and D,,r are dependent upon heat treatment with spheroidized, the most permeable, and
quenched. the least permeable. Annealed and normalized yield intermediate values of
permeation rate and diffusivity.
The decrease in permeation rate and diffusivity in the steel with the higher carbon
content is explained in terms of Fe3C acting as an obstacle to steady-state and unsteady-
state transport. Diffusivity also decreases as the carbide distribution becomes more finely
divided. Least permeation rate and diffusivity for medium carbon martensitic structure are
due to the amount of imperfection induced and a bet structure supersaturated with carbon
after quenching. which delay the hydrogen diffusion and obstruct the hydrogen flux.
Fig. I. Mild steel (a) blank specimen. and after cathodic charging with a constant charging current
density (5 mA cm-‘) at 25-C for (b) 60 s, (c) 90 s and (d) 120 s.
Hydrogen transport in carbon steels 243
Fig. 2. Normalized S45C steel, (a) blank specimen and (b) preferential hydrogen diffusion path
along carbide-ferrite interface after cathodic charging. (c) No preferential diffusion paths by prior
austenite grain boundaries were observed.
have much larger grain boundary diffusivity than lattice diffusivity.‘4,15 Accelerated
diffusion along grain boundaries was not detected in low carbon steel.
Normalized S45C medium steel has a fine pearlite and ferrite structure (Fig. 2(a)), where
a preferential localization of silver grains is observed at the carbide-ferrite interface after
cathodic charging with a constant current density (10 mA cm-*) for 3 min in Figs 2(b)-2(c).
No preferential diffusion paths by prior austenite grain boundaries were found in cathodic
charged specimens in Fig. 2(c). The blank specimens also did not show any silver grains. A
distinct aggregation of silver grains is visible at the interface between carbide and ferrite in
spheroidized S45C steel after the same charging condition (Fig. 3). These results indicate
that the preferential hydrogen diffusion path is along the interface between carbide and
ferrite. Hydrogen diffusivity for the quenched S45C steel is extremely slow due to the
martensitic specimen with high dislocation density and lath interfaces offering more sites for
hydrogen trapping. Few and fine silver grains were observed at lath interfaces after cathodic
charging with constant charging current density (10 mA cm-*) in 0.1 N NaOH even with a
hydrogen promoter at 25°C for 15 min and shown in Fig. 4.
Solubility
The ratio J,L/D,r or C,,, is calculated from equation (4) and appears to be lowest for
the spheroidized microstructure, intermediate for pearlitic microstructure and highest for
the quench microstructure. The increase in C,,, is an indication that trapping is dominant in
these microstructures. The apparent solubility increases with an increase in carbon content
Fig. : Spheroldtzed S4SC steel (a) blank qwc~men and (b) sliver grains are mostly vistble at the
Intcriace between carhide and ferrite after cathodic charging.
CONCLCTSIONS
Acknon,le~~enzenfs-The authors are grateful for the support of this research by the National Science Council,
Taiwan. under Contract No. NSC 83-040%EOl9-003.
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