Designation: G 148 – 97 (Reapproved 2003)

Standard Practice for

Evaluation of Hydrogen Uptake, Permeation, and Transport
in Metals by an Electrochemical Technique1
This standard is issued under the fixed designation G 148; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1. Scope 3.1.1 charging,, n—method of introducing atomic hydrogen

1.1 This practice gives a procedure for the evaluation of into the metal by galvanostatic charging (constant charging
hydrogen uptake, permeation, and transport in metals using an current), potentiostatic charging (constant electrode potential),
electrochemical technique which was developed by De- free corrosion, or gaseous exposure.
vanathan and Stachurski.2 While this practice is primarily 3.1.2 charging cell,, n—compartment in which hydrogen
intended for laboratory use, such measurements have been atoms are generated on the specimen surface. This includes
conducted in field or plant applications. Therefore, with proper both aqueous and gaseous charging.
adaptations, this practice can also be applied to such situations. 3.1.3 decay current,, n—decay of the hydrogen atom oxi-
1.2 This practice describes calculation of an effective diffu- dation current due to a decrease in charging current.
sivity of hydrogen atoms in a metal and for distinguishing 3.1.4 Fick’s second law,, n—second order differential equa-
reversible and irreversible trapping. tion describing the concentration of diffusing specie as a
1.3 This practice specifies the method for evaluating hydro- function of position and time. The equation is of the form
gen uptake in metals based on the steady-state hydrogen flux. ]C~x,t!/]t 5 ]/]xD 1]/]x@C~x,t!# for lattice diffusion in one
1.4 This practice gives guidance on preparation of speci- dimension where diffusivity is independent of concentration.
mens, control and monitoring of the environmental variables, See 3.2 for symbols.
test procedures, and possible analyses of results. 3.1.5 hydrogen flux,, n—the amount of hydrogen passing
1.5 This practice can be applied in principle to all metals through the metal specimen per unit area as a function of time.
and alloys which have a high solubility for hydrogen, and for The units are typically concentration per unit area per unit
which the hydrogen permeation is measurable. This method time.
can be used to rank the relative aggressivity of different 3.1.6 hydrogen uptake,, n—the concentration of hydrogen
environments in terms of the hydrogen uptake of the exposed absorbed into the metal (for example, g/cm3 or mol/cm3).
metal. 3.1.7 irreversible trap,, n—microstructural site at which a
1.6 This standard does not purport to address all of the hydrogen atom has a infinite or extremely long residence time
safety concerns, if any, associated with its use. It is the compared to the time-scale for permeation testing at the
responsibility of the user of this standard to establish appro- relevant temperature, as a result of a binding energy which is
priate safety and health practices and determine the applica- large relative to the migration energy for diffusion.
bility of regulatory limitations prior to use. 3.1.8 reversible trap,, n—microstructural site at which a
hydrogen atom has a residence time which is greater than that
2. Referenced Documents for the lattice site but is small in relation to the time to attain
2.1 ASTM Standards: steady-state permeation, as a result of low binding energy.
G 96 Guide for Online Monitoring of Corrosion in Plant 3.1.9 mobile hydrogen atoms,, n—hydrogen atoms that are
Equipment (Electrical and Electrochemical Methods)3 associated with sites within the lattice.
3.1.10 oxidation cell,, n—compartment in which hydrogen
3. Terminology atoms exiting from the metal specimen are oxidized.
3.1 Definitions: 3.1.11 permeation current,, n—current measured in oxida-
tion cell associated with oxidation of hydrogen atoms.
1
3.1.12 permeation transient,, n—the increase of the perme-
This practice is under the jurisdiction of ASTM Committee G01 on Corrosion
of Metals and is the direct responsibility of Subcommittee G01.11 on Electrochemi-
ation current with time from commencement of charging to the
cal Measuremnents in Corrosion Testing. attainment of steady state, or modification of charging condi-
Current edition approved Apr. 10, 1997. Published January 1998. tions (that is, rise transient). The decrease of the permeation
2
Devanathan, M.A.V. and Stachurski, Z., Proceedings of Royal Society, A270, current with time resulting from a decrease in charging current
90–102, 1962.
3
Annual Book of ASTM Standards, Vol 03.02. (that is, decay transient).

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 G 148 – 97 (2003)
3.1.13 recombination poison, n—chemical specie present atoms diffuse through the membrane and are then oxidized on
within the test environment in the charging cell which en- exiting from the other side of the metal in the oxidation cell.
hances hydrogen absorption by retarding the recombination of 4.3 The conditions (for example, environment and the
hydrogen atoms adsorbed onto the metal surface into hydrogen electrode potential) on the oxidation side of the membrane are
gas. controlled so that the metal surface is either passive or immune
3.2 Symbols: to corrosion. The background current established under these
3.2.1 For the purposes of this practice the following sym- conditions prior to hydrogen transport should be relatively
bols apply: constant and small compared to that of the hydrogen atom
oxidation current.
4.4 The electrode potential of the specimen in the oxidation
A = exposed area of specimen in the oxidation cell
cell is controlled at a value sufficiently positive to ensure that
(cm2)
C(x,t) = lattice concentration of hydrogen as a function of the kinetics of oxidation of hydrogen atoms are limited by the
position and time (mol/cm 3) flux of hydrogen atoms, that is, the oxidation current density is
C0 = sub-surface concentration of atomic hydrogen at diffusion limited.
the charging side of the specimen (mol/cm3) 4.5 The total oxidation current is monitored as a function of
Deff = effective diffusivity of atomic hydrogen, taking time. The total oxidation current comprises the background
into account the presence of reversible and irre- current and the current resulting from oxidation of hydrogen
versible trapping (cm2/s) atoms. The latter is the permeation current.
Dl = lattice diffusion coefficient of atomic hydrogen 4.6 The thickness of the specimen is selected usually to
(cm2/s) ensure that the measured flux reflects volume (bulk) controlled
F = faraday’s constant (9.6485 x 104 coulombs/mol) hydrogen atom transport. Thin specimens may be used for
I(t) = time dependent atomic hydrogen permeation cur- evaluation of the effect of surface processes on hydrogen entry
rent (µA) or exit (absorption kinetics or transport in oxide films).
Iss = steady-state atomic hydrogen permeation current 4.7 In reasonably pure, defect-free metals (for example,
(µA) single crystals) with a sufficiently low density of microstruc-
J(t) = time-dependent atomic hydrogen permeation flux tural trap sites, atomic hydrogen transport through the material
as measured on the oxidation side of the specimen is controlled by lattice diffusion.
(mol/s/cm2) 4.8 Alloying and microstructural features such as disloca-
Jss = atomic hydrogen permeation flux at steady-state
tions, grain boundaries, inclusions, and precipitate particles
(mol/s/cm2)
may act as trap sites for hydrogen thus delaying hydrogen
J(t)/Jss = normalized flux of atomic hydrogen
L = specimen thickness (cm) transport. These traps may be reversible or irreversible depend-
t = time elapsed from commencement of hydrogen ing on the binding energy associated with the particular trap
charging (s) sites compared to the energy associated with migration for
tb = elapsed time measured extrapolating the linear hydrogen in the metal lattice.
portion of the rising permeation current transient 4.9 The rate of hydrogen atom transport through the metal
to J(t) = O (s) during the first permeation may be affected by both irreversible
tlag = time to achieve a value of J(t)/Jss = 0.63 (s) and reversible trapping as well as by the reduction of any
x = distance into specimen from the charging surface oxides present on the charging surface. At steady state all of the
measured in the thickness direction (cm2). irreversible traps are occupied. If the mobile hydrogen atoms
t = normalized time (D1t/L2) are then removed and a subsequent permeation test conducted
t lag = Normalized time to achieve a value of j(t)/Jss = on the specimen the difference between the first and second
0.63 (s) permeation transients can be used to evaluate the influence of
irreversible trapping on transport, assuming a negligible role of
4. Summary of Practice oxide reduction.
4.1 The technique involves locating the metal membrane 4.10 For some environments, the conditions on the charging
(that is, specimen) of interest between the hydrogen charging side of the specimen may be suitably altered to induce a decay
and oxidation cells. In the laboratory, the charging cell contains of the oxidation current after attainment of steady state. The
the environment of interest. Hydrogen atoms are generated on rate of decay will be determined by diffusion and reversible
the membrane surface exposed to this environment. In field or trapping only and, hence, can also be used to evaluate the effect
plant measurements, the wall of the pipe or vessel can be used of irreversible trapping on transport during the first transient.
as the membrane through which measurement of hydrogen flux 4.11 Comparison of repeated permeation transients with
are made. The actual process environment is on the charging those obtained for the pure metal can be used in principle to
side of the membrane which eliminates the need for a charging evaluate the effect of reversible trapping on atomic hydrogen
cell. See 7.1 for guidance on various specimen configurations. transport.
4.2 In gaseous environments, the hydrogen atoms are gen- 4.12 This practice is suitable for systems in which hydrogen
erated by adsorption and dissociation of the gaseous species. In atoms are generated uniformly over the charging surface of the
aqueous environments, hydrogen atoms are produced by elec- membrane. It is not usually applicable for evaluation of
trochemical reactions. In both cases, some of the hydrogen corroding systems in which pitting attack occurs unless the

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 G 148 – 97 (2003)
charging cell environment is designed to simulate the localized 6.2 Non-metallic materials which are inert to the test envi-
pit environment and the entire metal charging surface is active. ronment should be used for cell construction.
4.13 This practice can be used for stressed and unstressed 6.2.1 At temperatures above 50°C, leaching from the cell
specimens but testing of stressed specimens requires consider- material (for example, silica dissolution from glass in some
ation of loading procedures. environments) can modify the solution chemistry and may
influence hydrogen permeation.
5. Significance and Use 6.2.2 Polytetrafluoroethylene (PTFE) is an example of a
5.1 The procedures described, herein, can be used to evalu- material suitable for elevated temperatures up to about 90°C.
ate the severity of hydrogen charging of a material produced by 6.2.3 Where metallic chambers are necessary (for contain-
exposure to corrosive environments or by cathodic polariza- ment of high pressure environments), the materials chosen
tion. It can also be used to determine fundamental properties of shall have a very low passive current to ensure minimal effect
materials in terms of hydrogen diffusion (for example, diffu- on the solution composition and shall be electrically isolated
sivity of hydrogen) and the effects of metallurgical, processing, from the membrane.
and environmental variables on diffusion of hydrogen in
metals. 6.3 The O-ring seal material should be selected to minimize
5.2 The data obtained from hydrogen permeation tests can possible degradation products from the seals and contamina-
be combined with other tests related to hydrogen embrittlement tion of the solution. This problem is particularly of concern
or hydrogen induced cracking to ascertain critical levels of with highly aggressive environments and at high test tempera-
hydrogen flux or hydrogen content in the material for cracking tures.
to occur. 6.4 Double junction reference electrodes may be used where
necessary to avoid contamination of test solutions. At elevated
6. Apparatus temperatures, the use of a solution conductivity bridge arrange-
ment with suitable inert materials is recommended.
6.1 The experimental set-up shall consist of a separate
charging and oxidation cell of a form similar to Fig. 1. Sealed 6.5 The location of the reference electrode in each compart-
oxidation cells, in which an additional material (usually palla- ment shall ensure minimal potential drop between the speci-
dium), either plated or sputter deposited onto or clamped men and the reference electrode. A Luggin capillary may be
against the specimen and the flux exiting this additional useful in cases where the solution resistivity is high, small cell
material is measured may be used provided that it is demon- volumes are used and long tests are conducted. See Guide G 96
strated that the introduction of this additional interface has no for further guidance.
effect on the calculated diffusivity. The clamping of this 6.6 Recording of oxidation (and, as appropriate, charging)
additional material may provide inaccurate permeation currents current shall be made using a standard resistor and a high
in some systems due to the barrier effect at the interface (that internal impedance digital voltmeter or by direct measurement
is, oxides, air gaps and so forth will act as a diffusion barrier). using a current monitoring device.

NOTE 1—A Luggin capillary should be used for more accurate measurement of potential when the current is large.
FIG. 1 PTFE Hydrogen Permeation Cell (with double junction reference electrodes, used for electrochemical charging)

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 G 148 – 97 (2003)
6.7 The measurement devices should be traceable to na- in appropriate cases where surface machining is difficult and
tional standards and calibrated prior to testing. may produce excessive cold working damage. However, elec-
6.8 In some cases, stirring of the solution in the charging tropolishing may induce hydrogen into the metal and may
cell may be required. This should be performed using suitable require the use of a low temperature heat treatment to reduce
stirring motor and apparatus the amount of hydrogen in the metal prior to testing.
7.2.8 After polishing, the specimen shall be cleaned in
7. Specimen
non-chlorinated solvents to remove traces of polishing chemi-
7.1 Design—Specimens may be in the form of plate or pipe. cals and degreased.
The dimensions shall enable analysis of the permeation tran- 7.2.9 The final thickness shall be measured in at least five
sient based on one-dimensional diffusion. For example, for locations in the exposed region of the membrane. The speci-
plates with a circular exposed area, the radius exposed to the men shall then be degreased in a suitable non-chlorinated
solution should be sufficiently large relative to thickness. A solvent and stored in a dry environment or a dessicator.
ratio of radius to thickness of 10:1, or greater, is recommended. 7.2.10 Coating of the exit surface of the specimen with
This condition may be made less stringent if the exposed area palladium or some other suitable material (for example nickel)
in the oxidation side is smaller than that on the charging side. to reduce the background current shall be undertaken at this
A ratio of radius to thickness of 5:1 is acceptable if the radius stage, if required.
of the exposed area on the oxidation side is reduced to 90 % of [Link] A thin palladium coating which does not resist
the area of the charging side. For pipes, the ratio of the outer through put of hydrogen is sometimes applied to one or both
radius to the inner radius should be less than 1:1 if the sides of the membrane following initial removal of oxide films
experimental results are to be analyzed based on the equations for the protection of the membrane.
for planar diffusion. Other specimen configurations may be [Link] A palladium coating on the charging face of the
used if limited by material form or equipment configuration. membrane will affect the sub-surface hydrogen concentration
However, it should be realized that such conditions may limit in the substrate and the measured permeation current. It is
the rigorous analysis of the data thus resulting in only important to verify that the calculated diffusivity is not
qualitative information. However, in some cases, this may be influenced by the coating. Electrochemical methods of forming
sufficient to rank the influence of various environmental or the coating can introduce hydrogen atoms into the material and
material variables on hydrogen charging severity. may influence the subsequent permeation measurements. Ar-
7.2 Preparation: gon etching of the surface followed by sputter coating with
7.2.1 Hydrogen atom permeation may be influenced by palladium can avoid this problem. Palladium coating is par-
microstructural orientation. The form of the original material ticularly useful for gaseous charging.
should be indicated (for example, bar or plate) and the location [Link] Palladium coating of the oxidation side of the
and orientation of the specimen relative to that of the original specimen can enhance the rate of oxidation and, thereby,
material should be defined. enable attainment of transport limited oxidation of hydrogen
7.2.2 The manufacture of sheet specimens should be con- atoms at less positive potentials than for the uncoated speci-
sidered carefully. Various methods of machining may be used men.
including electrochemical discharge machining (EDM) and
7.2.11 A suitable electrical connection shall be made to the
mechanical cutting.
specimen remote from the active areas.
7.2.3 EDM is particularly useful for preparing slices of
7.2.12 The specimen shall be uniquely identified. Stamping
material but may introduce hydrogen into the metal. Although
or scribing on the specimen remote from the active areas is
hydrogen dissolved in lattice sites or reversible trap sites may
recommended.
be lost subsequent to EDM, hydrogen atoms may be retained in
irreversible trap sites. The amount of hydrogen generated and
8. Test Environment
the extent of ingress into the metal will depend on the details
of the EDM process and the material characteristics, but 8.1 The test environment shall be relevant to the intended
sufficient material should be removed by subsequent machin- application, where applicable, or otherwise the environment
ing to ensure that all residual hydrogen atoms are removed. should be chosen to facilitate ease and reliability of making
7.2.4 Slices of material can be prepared by fine mechanical hydrogen permeation measurements. Suggestions for suitable
cutting and this method is preferred. systems for the latter case are given in Appendix X1.
7.2.5 Sheet specimens shall be machined to the required 8.2 The environments in the charging cell should be of
thickness. Care should be taken in machining to minimize purity for the intended purpose.
surface damage. 8.3 The environment in the oxidation cell shall be prepared
7.2.6 The thickness of the specimen in the region of interest using recognized analytical grade chemicals and distilled or
shall be as uniform as possible with a maximum variation not deionized water of purity sufficient to avoid unintentional
greater than 6 5 %. contamination.
7.2.7 The oxidation side of the specimen shall be mechani- 8.4 If the environment in the charging cell is aqueous, the
cally polished to a repeatable finish. A 600 grit surface finish is solution shall be either that directly used in service or a
recommended. The charging side may be similarly treated or laboratory environment prepared with the purity as indicated in
used in condition similar to the service condition being 8.3. Gaseous environments should simulate those for the
modeled. Electropolishing of specimens may also be employed intended application.

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 G 148 – 97 (2003)
8.5 In some cases for which higher purity of the charging 9. Test Procedure
solution is desirable, the solution may be prepared using
9.1 The specimen shall be prepared to desired surface finish
appropriate high purity analytical grade chemicals or pre-
and the thickness measured.
electrolysis may be employed. Pre-electrolysis can be used to
remove certain cationic contaminants by cathodic deposition 9.2 The solutions shall be prepared and pre-electrolysis
and usually involves applying a voltage difference between two carried out where desirable.
platinum electrodes in the solution of interest. The area of the 9.3 The pH of the solutions should be measured, if appro-
cathode should be as large as reasonable to enhance the rate of priate (see 10.1).
removal of contaminants. 9.4 The reference electrodes shall be checked against at
8.6 A volume of solution to metal area ratio greater than 20 least one, and preferably two, other reference electrodes and
ml/cm2 is usually adequate. The volume of solution in the shall be accurate to 65 mV. The choice of reference electrode
oxidation chamber need not be particularly large since the is optional.
extent of reaction is usually relatively small. 9.5 The two-compartment cell shall be put together with
8.7 The volume of solution in the charging cell depends on seals as appropriate. The cell assembly shall be connected to
the particular choice of environment and the extent of reaction the electronic measuring apparatus as shown in Fig. 2.
on the specimen. Poisons added to enhance hydrogen entry 9.6 The solution for the oxidation cell shall be added to the
may be consumed with time. The volume of solution shall be relevant chamber and vigorous purging with a suitable inert gas
sufficient to minimize changes in solution composition during
should be commenced to deaerate the solution quickly, even if
the course of the experiment, or periodic replenishment shall
deaerated previously to minimize aeration during solution
be used, as needed, to maintain the consumable species within
transfer. The potential shall be set to the control value (+ 300
suitable levels within the charging cell.
mV SCE is typical for several metals exposed to 0.1M NaOH
8.8 Flow of solution in the charging cell can affect the local
(see 9.12). The magnitude of the background oxidation (pas-
environment at the surface in some cases. Where solution flow
sive) current will depend on the system but values lower than
is relevant to a service condition, the flow conditions shall be
0.1 µA/cm 2 are usually readily attainable.
simulated or testing should be conducted to enable repeatable
conditions, whether using stirrers or vigorous purging or slow 9.7 The time at which the environment is added to the
bubbling where the gas purge tube has been positioned close to charging cell depends on the characteristics of the system but,
the specimen. ideally, addition of the environment should be made after the
8.9 Variations in the pH of the charging solution during a oxidation current has achieved a steady, low value. In some
permeation transient may influence the form of the transient, cases, aqueous solution may be added to the charging cell prior
even under constant charging current, because of its influence to the establishment of the steady-state oxidation current
on surface films. provided that exposure does not generate significant hydrogen,
8.10 The temperature of the solution typically has a signifi- for example, a passivating system with a very low passive
cant effect on hydrogen permeation. The temperature of the current.
solutions in charging and oxidation cells should be nominally 9.8 In testing at elevated temperature, care should be taken
the same and maintained constant to 6 0.5°C for the period of to minimize thermal shock when adding the solution to the
the experiment. Any variation should be recorded. This may be charging side as this can sometimes result in significant
achieved using a temperature-controlled room or, in the case of perturbation of the passive current in the oxidation cell.
small cells, by heating or cooling the outside of the cell with a 9.9 If the solution is to be deaerated, this shall be done prior
thermostatically controlled fluid. In the latter case, when the to addition to the charging cell or deaeration should commence
charging compartment is refreshed continuously from a reser- by vigorous purging on addition of the solution to the charging
voir using a recirculation system, the temperature of the cell to remove oxygen quickly depending on the sensitivity of
solution in the reservoir should be controlled carefully to the environment or material to oxygen contamination. Deaera-
minimize temperature gradients across the specimen. tion shall be continued during the test as required.

FIG. 2 Electrochemical Hydrogen Permeation Cell Assembly and the Measuring Apparatus

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 G 148 – 97 (2003)
9.10 The stirring motor should be switched on, where used. complete interpretation of subsequent increasing permeation
For non-passivating systems galvanostatic charging or poten- transients. This consideration applies also to tests in which step
tiostatic charging shall commence on exposure of the speci- increases in charging current are made (see 10.16). Irreversible
men. trapping will not be detected using this procedure if the traps
9.11 For measurement of hydrogen permeation, the total are already full (for example, from material processing) prior
oxidation current (comprising background passive current and to the first permeation study.
atomic hydrogen oxidation or permeation current) shall be 9.16 The charging current may be reduced by reducing the
monitored versus time until steady-state is achieved. applied current or potential or by changing the environment. If
9.12 The electrode potential of the specimen exposed to the it is intended to analyze the decay current, the requirement for
oxidation compartment shall be chosen to ensure bulk a defined boundary condition in analyzing the transient, means
transport-limited kinetics for oxidation of hydrogen atoms. In a that the conditions on the charging side should be such as to
preliminary test, and ideally for the test conditions for which oxidize or reombine the hydrogen at its transport limited rate.
the oxidation current is largest, the control potential on the 9.17 Repetitive permeation transients may also be generated
oxidation side should be increased and the incremental current for some systems by withdrawing the specimen after attain-
monitored. An initial increase in current will be obtained but ment of steady-state permeation and allowing the hydrogen
for transport-limited kinetics this should subsequently decrease atoms to diffuse out. Elevated temperature baking may also be
to a steady-state value equivalent to that obtained prior to the used to accelerate removal, provided this produces no micro-
change in potential. If the steady current at the new potential is structural changes. The specimen surface may then be repol-
significantly higher, the electrode potential should be increased ished, cleaned, and the permeation procedure repeated.
progressively until the steady current at each potential becomes 9.18 The final pH of the solutions should be measured if
independent of potential. This condition will define the control appropriate 10.1).
potential for the system. 9.19 The final thickness of the specimen shall be measured
9.13 In aqueous solutions, the exposure conditions on the if significant corrosion has occurred.
charging side of the membrane may be chosen to represent a 9.20 Replicate tests should be conducted to determine
particular service situation involving corroding conditions or repeatability of the measurements for the particular test con-
the conditions may be selected to maintain constancy of the ditions used.
sub-surface hydrogen concentration. 9.21 Unless the thickness of the specimen represents a
9.13.1 For characterization of hydrogen transport in the particular service application or required test condition, tests
bulk of the material, galvanostatic charging is preferred. For should be performed on at least three different specimen
reliable measurement, only minor changes in potential during thicknesses. With increasing thickness of specimen, the signifi-
testing should occur. Significant variation in potential indicates cance of surface processes on the rate of transport will be
changing surface state and unsteady boundary conditions diminished with respect to transport through the bulk of the
which render uncertain the interpretation of the permeation material. These tests will indicate the relative extent to which
transients. the transport of hydrogen is controlled by transport through the
bulk of the material, or by surface processes, for example,
9.13.2 Potentiostatic charging may also be used provided
absorption kinetics or transport through an oxide film.
there are no significant variations in the current.
9.13.3 Variations immediately following exposure do not 10. Environmental Control and Monitoring
necessarily have an important influence on the permeation 10.1 For galvanostatic/potentiostatic tests in very acid or
transient provided that the duration is short compared to the alkaline solutions (0.1 M or greater), environmental variations
overall time of the transient. during a test are often negligible, assuming that significant
9.14 In many cases, the measurements of permeation cur- corrosion is not allowed to occur. In near-neutral solutions, pH
rent versus time are useful in characterizing the severity of changes may occur and the pH should be measured before and
hydrogen charging. The parameters that should be noted are after a test.
Jmax and Jss for the conditions being examined. In cases where 10.2 For reliable interpretation of hydrogen permeation
Jss is much less than Jmax, the indications are (a) formation of measurements, the surface condition in the charging cell
protective films on the charging surface of the membrane should remain constant during a test. However, in some cases,
which impede hydrogen permeation, (b) formation of internal changing corrosion conditions (for example, due to film
voids, blisters, or internal hydrogen induced cracking or (c) formation) make it impossible to obtain constant charging
depletion of species in the charging solution such as recombi- conditions. For this reason, monitoring of the electrode poten-
nation poisons. tial is useful in galvanostatic tests because it gives an indication
9.15 To distinguish the effects of irreversible and reversible of changing surface state. Similarly, monitoring of the current
trapping on hydrogen transport, the charging current should be is important in potentiostatic tests.
reduced to zero and sufficient time allowed for hydrogen atoms 10.3 For tests in which H2S gas is bubbled through the
in interstitial lattice sites and reversible trap sites to exit. solution, monitoring of dissolved H2S content of the solution
Monitoring of the permeation current will indicate when all the by sampling and measurement should be conducted. Unless the
mobile hydrogen has been removed. If the charging current is purpose of the test is to define transient behavior, sufficient
not reduced to zero and, consequently, a permeation current time shall be allowed for equilibrium to be obtained prior to
remains, a residual concentration gradient exists and this will exposure of the test specimen.

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 G 148 – 97 (2003)
10.4 For tests with other recombination poisons, it is rec- In the slope method, the effective diffusivity can be calcu-
ommended that sampling of the charging solution be per- lated from the slope of a plot of log(|Jss–J(t)|) versus 1/t which
formed before and after permeation tests are made, at least is linear with a slope of L2log (e)/4D.
once, for the particular experimental conditions being evalu- 11.3.2 The values for Deff calculated by the two methods or
ated, to determine the extent of depletion of the poison that by curve fitting to the permeation transient shall be in agree-
occurred during the test. ment, if Fick’s second law is applicable.
11.3.3 To verify applicability of Fick’s second law to the
11. Procedures For Analysis of Results permeation transient, plot the permeation transient in the form
11.1 The background current associated usually with the of normalized flux (J(t)/Jss) against the logarithm of normal-
passive current of the oxidation cell shall be subtracted from ized time, t, where J(t) is calculated from
the measured oxidation current prior to analysis of both I~t! / A
steady-state and transient permeation currents. J~t! 5 F (5)
11.2 Analysis of the Steady-State Permeation Current:
11.3.4 Compare the normalized transient with that derived
11.2.1 The steady state permeation current ( Jss) gives
from Fick’s second law which for rising transients is given by
information on the subsurface concentration of hydrogen atoms
at the charging surface as follows:
`
J~t!
Jss / A D1 C0
Jss 5 F 5 L (1) J ss 5 1 1 2 (
n51
~–1!n exp ~–n2p2t! (6)

where:
For highly alloyed metals and for multiphase metals, Eq 1 t = Deff t/L2
may be inadequate. In highly alloyed metals, the lattice A summation from n = 1 to 6 is sufficiently accurate and in
diffusion coefficient (D1) may vary greatly from that of the many cases n = 3 is acceptable.
primary element (for example, iron in corrosion resistant 11.3.5 If the permeation transient is steeper than predicted
steels). In multiple materials (for example, in duplex stainless from Fick’s second law, this indicates that trap occupancy is
steels) diffusion path tortuosity and alternative diffusion paths significant. A permeation transient which is less steep than
through the material may need to be considered or an appro- predicted from Fick’s second law is often an indication of
priate value of D1 utilized. unsteady surface conditions. If volume-controlled transport is
11.2.2 A plot of Jss against reciprocal thickness should be of primary interest, this test should be repeated with increased
linear for volume controlled transport although this requires specimen thickness to confirm the results.
that the C0 value in the separate experiments be identical. 11.3.6 If the first permeation transient takes longer than the
11.2.3 When reversible trapping only is important and when second permeation transient, that is the normalized permeation
the permeation transient for this case can be represented by curves are displaced to longer times (see Fig. 3 in Appendix
Fick’s first law, then X1), it can be deduced that irreversible traps exist and affect
Deff C0 permeation.
Jss 5 L (2) 11.3.7 In the absence of void or blister formation or hydro-
gen induced cracking, the second and subsequent transients
11.2.4 For some systems a peak in the transient may be should show the same permeation behavior provided the C0
observed and a steady current may not be attained. This can be values are similar.
due to the development of voids in the material or changes, or 11.3.8 An effective diffusion coefficient may be calculated
both, in surface film (for example, build up of corrosion for transients steeper than that associated with Fick’s second
product) on the charging side of the specimen. law using Eq 3 but it has no theoretical basis since the
11.3 Analysis of Permeation Transient steepness of the permeation transient indicates a changing
11.3.1 The effective diffusion coefficient can be calculated effective diffusivity with time. Hence, values based on tlag and
based on the elapsed time (tlag) at J(t)/J ss= 0.63, the break- tb will differ. For comparative purposes, it is recommended that
through time (tb) or the slope method.4 For the calculation the calculation based on t lag should be quoted.
based on the elapsed time the following equation should be 11.3.9 Analysis of second and subsequent transients, which
used: are steeper than predicted by Fick’s second law, may be carried
out to quantify the binding energy and the density of reversible
L2 D1
Deff 5 6t 5 6t (3) trap sites. However, the analysis is non-trivial and involves
lag lag
numerical solution of mass conservation equations incorporat-
The effective diffusivity based on breakthrough time is given ing diffusion and reversible trapping with the trap occupancy
by the following equation: term incorporated.
L2 D1 11.3.10 Analysis of first permeation transients which are
D eff 5 15.3t 5 15.3t (4) steeper than Fick’s second law should account for both
b b
reversible and irreversible traps and this, also, necessitates
numerical analysis.
4
McBreen, J., Nanis, L., and Beck, W., Journal of Electrochemical Soc., Vol 113, 11.3.11 When peaks in the transients are observed (see
1966, pp. 1218–1222. 11.2.4), this implies the value of the effective diffusivity is also

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 G 148 – 97 (2003)

NOTE 1—Rising permeation transients for BS 970 410S21 stainless steel in acidified NaCl at 77°C. Results show irreversible trapping (1st transient)
and dependency on charging conditions (C0 value). Note the time of delay and steepening of the curves relative to lattice diffusion (Fick’s law), the
similarity of second and third transients and the independence of thickness.
FIG. 3 Permeation Transients

varying with time and analysis in uncertain, but Eq 3 may be degree of aeration, flow conditions, and temperature and final
used as an empirical estimate at J(t)/Jss = 0.63. values of these variables should be recorded. For tests in
11.3.12 In analyzing the results from step charging experi- aqueous solutions containing H2S, the initial and final concen-
ments, initial hydrogen flux shall be accounted for. A simple trations should be recorded.
subtraction may not be valid. An initial atomic hydrogen 12.1.7 For gaseous charging, the composition and purity of
concentration gradient exists in the metal and this renders the gas should be stated.
conventional analysis invalid unless the initial steady perme-
ation current is less than 5 % of the final steady current. More 12.1.8 The test procedure should be described with refer-
extensive analysis may be required. ence to the recommendations in Section 9.
12.1.9 The controlling electrode potential in the oxidation
12. Reporting cell in terms of the standard hydrogen electrode or a saturated
12.1 Report the following information: calomel electrode at 25°C. A Ag/AgCl electrode may also be
12.1.1 Test material characterization in terms of specifica- used provided the electrode solution is defined.
tion, product form, chemical composition, and heat treatment. 12.1.10 The electrochemical conditions in the charging cell
12.1.2 The orientation and location of the specimen relative and any variation during the test, for example, significant
to parent product. variation in electrode potential during galvanostatic charging.
12.1.3 Method of specimen preparation. 12.1.11 The method of obtaining repeat transients.
12.1.4 Average thickness of specimen and exposed area in
12.1.12 The appearance of the surfaces of the specimen
charging and oxidation cells. Average thickness of specimen
after testing if changed significantly from the initial condition.
after test, if changed. If the distribution of the thickness (see
7.2.6 and 7.2.9) is outside the recommended range, the 12.1.13 The form of the data output is optional but shall
individual measured values should be reported. include at least the background passive current density and the
12.1.5 Description of the environment chamber and the steady-state permeation current density or the C0 value. The
volume of solution in the charging and oxidation cells. For lattice diffusivity used in Eq 1 to calculate C0 shall be reported.
gaseous charging, the pressure of the gas in the charging The effective diffusion coefficient may also be reported but its
compartment should be specified. method of determination should be quoted. The variability of
12.1.6 Initial solution composition and purity of solvent and the parameters should be indicated. A representative example
chemicals in both compartments. Where appropriate, pH, of J(t)/J ss or I(t)/Lss versus t or t should be included.

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 G 148 – 97 (2003)
12.1.14 The shape of the transient relative to the prediction
from Fick’s law should be noted and observation of any peak
in the transient should be reported.
13. Keywords
13.1 charging; decay current; diffusivity; electrochemistry;
flux; hydrogen; permeation; transient

APPENDIX

(Nonmandatory Information)

X1. SUGGESTED TEST CONDITIONS FOR SPECIFIC ALLOY TYPES

X1.1 General—This appendix gives examples of test con- 80°C is recommended. The acceptable specimen thickness
ditions suitable for measurement of hydrogen diffusivity and depends on the temperature and specific recommendations for
trapping within the volume of the material for alloy systems for this alloy type are not possible because of lack of data.
which a reliable range of data and testing experience are Nevertheless, the values of thickness recommended for the
available. duplex stainless steel would probably be more than adequate
for austenitic stainless steels and could be adopted initially.
X1.2 Stainless Steels:
X1.2.1 Martensitic Stainless Steel: X1.3 Nickel Alloys:
X1.2.1.1 The environment in both cells should be 0.1M X1.3.1 The test conditions should be those for duplex
NaOH. The potential in the oxidation cell should be set at about stainless steels.
+ 300 mV (SCE). Cathodic polarization with charging currents X1.3.2 The diffusivity of these face centered cubic alloys
of about 1 mA/cm2 can be used to generate hydrogen. On will be small compared to body centered cubic systems.
attainment of steady-state, the potential of the charging surface Accordingly, testing at elevated temperatures (for example,
can be set to + 300 mV (SCE). The permeation current will 80°C) may be preferred. Specimen thicknesses of 200 µm or
then decay to the passive current and the cathodic charging greater are recommended for pure nickel and 100 µm or greater
current can then be re-applied to generate a second permeation for Alloys 600 (NJS N06600), X-750 (UNS N07750), and 718
transient. (UNS N07718) at 80°C.
X1.2.1.2 An alternative approach to the cathodic polariza-
tion which generates much higher C0 values and permeation X1.4 Carbon, Carbon-manganese and Other Low Alloy
currents involves using acidified 0.5 M NaCl in the charging Steels :
cell. At a pH value of about 2.6, the oxide film is rapidly X1.4.1 0.1 M to 1 M NaOH is recommended for the
dissolved and charging is induced by the corrosion current. environment in the oxidation cell with the electrode potential
Subsequent transients can be obtained by removal of the set to + 300 mV (SCE). No specific recommendation can be
specimen and baking out the hydrogen overnight at about 80°C given for the environment in the charging cell. For example,
before retesting. cathodic charging in 0.1M NaOH leads to a transient surface
X1.2.1.3 Since the steel is ferritic, diffusivities are relatively state with permeation transients which are usually shallower
high and specimen thicknesses of about 250 µm or greater at than Fick’s law and not very repeatable. The transients can be
20°C and about 1 mm at 80°C are recommended. very prolonged with a slow drift to steady-state. Testing in acid
X1.2.2 Duplex Stainless Steel: solution can lead to the development of voids and a peak in the
X1.2.2.1 The environment in both cells should be 0.1M current transient which makes analysis difficult.
NaOH and the potential of the specimen in the oxidation cell X1.4.2 Palladium coating of the charging surface prior to
should be + 300 mV (SCE). Cathodic polarization with cathodic charging in 0.1M NaOH can minimize variations in
charging currents of about 1 mA/cm 2 can be used to generate surface conditions during the permeation transient and yield
hydrogen atoms. Subsequent transients can be determined by repeatable transients provided the specimen thickness is ad-
polarizing the charging surface to + 300 mV (SCE) before equate.
reapplying cathodic charging. X1.4.3 The effective diffusivity of low alloy steels can vary
X1.2.2.2 Specimens of 100 µm thickness are typically used by orders of magnitude depending on the material composition
at 20°C. At temperatures greater than 80°C, typical specimen and microstructure and general recommendations for the thick-
thickness used is 200 µm. ness of the specimen cannot be made. For tests at 20°C, the
X1.2.3 Austenitic Stainless Steel: specimen thickness can range from 1.0 mm to the order of
X1.2.3.1 The test conditions should be those for duplex centimeters.
stainless steel. Since the diffusivity of hydrogen in austenitic X1.4.4 Aqueous charging of low alloy steels in H 2S
stainless steel is very low, testing at a temperature of about environments may give rise to high values of the hydrogen

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 G 148 – 97 (2003)
permeation current. Depending on the thickness of specimen, repeatable data because of the increased efficiency of the
palladium coating of the oxidation surface may provide more hydrogen atom oxidation reaction.

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