This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

Designation: F1113 − 87 (Reapproved 2017)

Standard Test Method for

Electrochemical Measurement of Diffusible Hydrogen in
Steels (Barnacle Electrode)1
This standard is issued under the fixed designation F1113; 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 (´) indicates an editorial change since the last revision or reapproval.

1. Scope D1193 Specification for Reagent Water

1.1 This test method covers the procedure for measuring F519 Test Method for Mechanical Hydrogen Embrittlement
diffusible hydrogen in steels by an electrochemical method. Evaluation of Plating/Coating Processes and Service En-
vironments
1.2 This test method is limited to carbon or alloy steels, G3 Practice for Conventions Applicable to Electrochemical
excluding austenitic stainless steels. Measurements in Corrosion Testing
1.3 This test method is limited to flat specimens to which
the cell can be attached (see 4.6 and 4.8). 3. Summary of Test Method
1.4 This test method describes testing on bare or plated steel 3.1 A hydrogen-containing part is made the anode in an
after the plate has been removed (see 4.4). electrochemical cell. The diffusible (atomic) hydrogen, which
comes to the metal-electrolyte interface, is oxidized to protons
1.5 This test method is limited to measurements at room (H+); H+ combines with hydroxyl ions (OH− ) in the electrolyte
temperature, 20 to 25°C (68 to 77°F). to form water. The oxidation current is measured and related to
1.6 This standard does not purport to address all of the the hydrogen concentration.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 4. Significance and Use
priate safety and health practices and determine the applica- 4.1 The critical level of hydrogen in steels is that hydrogen
bility of regulatory limitations prior to use. which can build up to high concentrations at points of high
1.7 This international standard was developed in accor- triaxial stress causing embrittlement of the steel which can lead
dance with internationally recognized principles on standard- to catastrophic damage. This hydrogen can enter by various
ization established in the Decision on Principles for the means, such as during pickling and electroplating. Means of
Development of International Standards, Guides and Recom- reducing this hydrogen during processing are given in Speci-
mendations issued by the World Trade Organization Technical fication B766 and Practices B183 and B242. It is still
Barriers to Trade (TBT) Committee. necessary, however, to know how effective these methods are.
Though the ultimate reason for measuring this hydrogen is to
2. Referenced Documents relate it to embrittlement, this is not within the scope of this test
2.1 ASTM Standards:2 method. As susceptibility to hydrogen embrittlement is a
B183 Practice for Preparation of Low-Carbon Steel for function of alloy type, heat treatment, intended use,and so
Electroplating forth, the tolerance for hydrogen must be determined by the
B242 Guide for Preparation of High-Carbon Steel for Elec- user according to Method F519.
troplating 4.2 Though the actual hydrogen concentration is not deter-
B766 Specification for Electrodeposited Coatings of Cad- mined in this test method, the current densities have been
mium shown to be useful as an indication of relative hydrogen
concentrations (1-3),3 and therefore the degree of hydrogen
1
embrittlement (1,2). Thus, measurements can be compared to
This test method is under the jurisdiction of ASTM Committee F07 on
Aerospace and Aircraft and is the direct responsibility of Subcommittee F07.04 on one another (see 4.1 and 7.1).
Hydrogen Embrittlement.
4.3 This test method is applicable as a quality control tool
Current edition approved June 1, 2017. Published July 2017. Originally approved
in 1987. Last previous edition approved in 2011 as F1113 – 87 (2011). DOI: for processing (such as to monitor plating and baking) or to
10.1520/F1113-87R17. measure hydrogen uptake caused by corrosion.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on Boldface numbers in parentheses refer to the list of references at the end of this
the ASTM website. standard.

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

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 F1113 − 87 (2017)
4.4 This test method is nondestructive; however, if there is
a coating, it must be removed by a method which has been
demonstrated to neither damage the steel nor introduce hydro-
gen to make the measurement.
4.5 This test method is also applicable to situations produc-
ing continuous hydrogen permeation, such as high pressure
hydrogen cylinders or corrosion processes. The results,
however, would require a different treatment and interpretation
(4).
4.6 This test method is also applicable to small parts, such
as fasteners. The technique, procedure, and interpretation
would, however, have to be altered.
4.7 Use of this test method on austenitic stainless steels and
other face centered cubic (FCC) alloys would require different
measurement times and interpretation of results because of
differing kinetics.
4.8 This test method can be used on slightly curved surfaces
as long as the gasket defines a reproducible area. The area
calculation must, however, be changed.
5. Apparatus
5.1 Cell—A photo and drawing of a typical cell, which has
been found to be acceptable for hydrogen measurements, are
shown in Figs. 1 and 2, respectively.
5.1.1 The cell is made of a nonmetallic material that will not
react with or contaminate the solution. The side opening has a
recess to accommodate the silicone rubber gasket.
5.1.2 Gasket, silicone rubber, shall provide a reproducible
solution-contact area with the specimen, preferably 1.0 cm2.
5.1.3 Cell Holder, a cradle-like C-clamp. Other clamping
devices can be used if necessary, such as for larger parts.
5.1.4 Cathode, a nickel/nickel oxide electrode. It is made by FIG. 1 Photograph of Cell
removing the positive plate from a nickel/cadmium battery and
attaching a nickel wire or foil. The area of this cathode shall be
approximately five times that of the anode.
5.1.5 Anode—The anode is the specimen. all reagents shall conform to the specifications of the Commit-
5.1.6 The cell is left open to the atmosphere. No purging is tee on Analytical Reagents of the American Chemical Society,
used. where such specifications are available.4 Other grades may be
used, provided it is first ascertained that the reagent is of
5.2 Current Measuring Device—The current can be mea- sufficiently high purity to permit its use without lessening the
sured by any method that will not affect its value. A zero accuracy of the determination.
resistance ammeter (5), a current follower (6), and the current
measuring system shown in Fig. 3 (1) have been found to be 6.2 Purity of Water—Distilled or deionized water conform-
acceptable. The following description refers to Fig. 3. ing to Specification D1193, Type IV, shall be used to prepare
5.2.1 Standard Resistor, connected across the cell through a all solutions.
switch. 6.3 Sodium Hydroxide Solution (0.2M)—Dissolve 8 g of
5.2.2 Electrometer, to determine the current by measuring sodium hydroxide (NaOH) pellets in water and dilute to 1 L.
the voltage drop across the resistor. A 10-kΩ resistor with an 6.4 Ammonium Nitrate Solution (120 g/L)—Dissolve 120 g
electrometer having an input impedance of 1012 Ω and a 1-mA of ammonium nitrate (NH4NO3) in water and dilute to 1 L.
output has been found to be satisfactory.
5.2.3 Strip Chart Recorder, to monitor the electrometer 6.5 Methyl Alcohol (CH3OH).
output. A recorder having an input resistance of 100 kΩ has 6.6 Ethyl Alcohol (C2H5OH).
been found to be satisfactory.
5.2.4 Timer, accurate to within 10 s in a 30-min run.
4
Reagent Chemicals, American Chemical Society Specifications, American
6. Reagents Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, seeAnalar Standards for Laboratory
6.1 Purity of Reagents—Reagent grade chemicals shall be Chemicals, BDH Ltd., Poole, Dorset, U.K., and theUnited States Pharmacopeia and
used in all tests. Unless otherwise indicated, it is intended that National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.

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 F1113 − 87 (2017)
drain of the charge. To prevent this from happening, alternate two
electrodes during a series of measurements.
8.1.1 Charge the Ni/NiO electrode in a 0.2M NaOH solution
for 1⁄2 h at a current density of 5 to 10 mA/cm2.
8.1.2 The Ni/NiO electrode is made the anode, that is,
connected to the positive terminal of the charging source. Any
conductor that will not react with the solution, such as
platinum, graphite, or steel, may be used as the cathode.
8.2 Determine the specimen contact area which is outlined
by the gasket.
8.2.1 Assemble the cell with a smooth piece of aluminum
sheet or foil, at least 0.04 mm thick, between a specimen and
the gasket. The Ni/NiO electrode is not needed.
8.2.2 Fill the cell with 0.2M NaOH solution and allow the
aluminum to be etched by the alkaline solution for about 20
min.
8.2.3 Dismantle the cell and rinse well. A properly as-
sembled cell will produce a sharply defined, circular etch (see
Fig. 4).
8.2.4 Measure the diameter of the etched circle under a
microscope (10×), and calculate the area (see 10.2).
8.2.5 A poor gasket or improper tightening of the cell will
FIG. 2 Engineering Drawing of Cell (3) be detected by this procedure. Overtightening will produce a
deformation of the gasket, resulting in an out-of-round etch.
Undertightening, or a worn-out gasket, will cause crevices,
resulting in etching under the gasket (see Fig. 4).
8.3 Measure uncoated coupons, prepared in accordance
with 7.1, to determine the background current density. Keep
these coupons desiccated for at least one week before
measuring, to assure that no hydrogen, as a result of corrosion,
is produced, and to allow any hydrogen in the specimens to
escape.
NOTE 2—The background measurement is used only as a reference to
indicate the presence or absence of hydrogen. It is not used in any
calculation.

9. Procedure
FIG. 3 Schematic of Measuring Apparatus (1)
NOTE 3—This procedure pertains to cadmium-plated specimens. Any
other plating must be removable by a method that will neither damage the
steel nor introduce hydrogen.
7. Test Specimens
9.1 Specimen Preparation:
7.1 The test specimen can be a coupon of 1- to 6-mm
thickness or an actual part. If it is a coupon, it shall be of the NOTE 4—The time to prepare the specimen must take no longer than 5
min.
same alloy, form, temper/condition, and surface finish as the
part. The specimen shall be of sufficient size to accommodate 9.1.1 Remove any cadmium plate from an area on one side
the cell and of sufficient smoothness and flatness to prevent of the specimen large enough to accommodate the cell (ap-
leaking of the electrolyte under the gasket (see 8.2). If possible, proximately 40 by 40 mm) by swabbing with ammonium
specimens shall be of sufficient size for a duplicate measure-
ment to be made (see 9.4).

8. Calibration and Standardization

8.1 Calibrate the nickel/nickel oxide (Ni/NiO) electrode
against a saturated calomel electrode (SCE) in 0.2M NaOH. A
freshly charged Ni/NiO electrode will be at least 350 mV
positive to the SCE when measured according to Practice G3.
It shall be recharged when its potential is less than 300 mV
positive to the SCE. FIG. 4 Etched Areas (NaOH on Al) Showing (A) Good Gasket Fit
and (B) Poor Fit Showing Undercutting of Gasket as a Result of
NOTE 1—Repeated use of the Ni/NiO electrode will cause a temporary Undertightening or Worn Gasket

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 F1113 − 87 (2017)
nitrate solution. Rinse with water and dry. Swabs made of
polyurethane foam or cotton have been found to be satisfac-
tory.
9.1.2 Abrade the surface lightly with an aluminum oxide-
impregnated nylon cleaning pad to remove surface contamina-
tion and to provide a reproducible surface finish. Wipe clean
using a tissue wet with methyl or ethyl alcohol.
9.2 Cell Assembly:
NOTE 5—The time to assemble the cell and start the measurement must
take no longer than 5 min. The total time from the start of 9.1.1 – 9.3.1
must take no longer than 10 min.
9.2.1 Clamp the Cell to the Specimen.
NOTE 6—The cell should be clamped only tight enough to prevent
leakage. Overtightening will cause deformation of the gasket. Proper
tightening can be determined by following the procedure in 8.2.
9.2.2 Clamp the Ni/NiO electrode in the center of the cell
cavity using the cell dimensions of Fig. 1. For other cell
designs, the distance between the electrodes shall be 25 mm.
9.2.3 Connect the resistor and switch between the Ni/NiO
electrode and the specimen.
9.2.4 Connect the electrometer across the resistor so that the
Ni/NiO electrode will measure positive and the steel negative.
9.2.5 Connect the recorder to the electrometer output.
9.2.6 Fill the cell with 0.2M NaOH, making sure that the
Ni/NiO electrode and the specimen measurement area are
completely covered with solution.
9.3 Making the Measurement:
NOTE 7—The measurement must be started within 1 min of filling the
cell. FIG. 5 Recorder Tracings Showing (A) Good Measurement, (B )
Acceptable Measurement, and (C ), Poor Measurement Which
9.3.1 Simultaneously turn on the cell switch and the timer. Must Be Repeated
NOTE 8—The oxidation current decreases with time. During the
measurement, it will change by a few orders of magnitude. Therefore, for 10. Calculation
the first 5 min, set the recorder at an appropriate high setting to prevent
overload. The final readings will be in the microampere range. Adjust the 10.1 Calculate the current from the voltage drop across the
electrometer and recorder accordingly. standard resistor using Ohm’s law, I = E ⁄R. For example, if the
9.3.2 Record the current at the end of 30 min. This shall be full-scale voltage on the strip chart recorder is 10 mV and the
referred to as the 30-min reading. resistance is 10 kΩ, then the full-scale current is 1 µA.

NOTE 9—The current measurement must always be made for the same
10.2 Calculate the contact area from the diameter of the
length of time. In this test method, 30 min has been chosen. The reasons etched surface (see 8.2). The diameter, D, should be measured
for this are given in references (1,3). in two directions and averaged. If it has been established that
9.3.3 Turn off the switch. the contact area is essentially round, the area, A, is given by:
9.3.4 Dismantle the cell, rinse, and dry. A = π (D/2)2. For example, if the average diameter is found to
be 1.2 cm, the area is 3.14 (1.2/2)2 or 1.10 cm2.
9.4 Repeat Measurements:
10.3 Current density is the current per unit area. For
NOTE 10—If the recorder tracing is poor (see Fig. 5), a repeat example, if the 30-min current is 0.66 µA, and the exposed area
measurement must be made. is 1.1 cm2, then the current density is 0.66/1.1 or 0.60µ A/cm2.
9.4.1 If cadmium-plated coupons or parts are of sufficient
size, make duplicate measurements on the same specimen, 11. Interpretation of Results
either alongside or opposite to the first in accordance with 9.1. 11.1 The 30-min current density will depend on the material
If alongside, the newly swabbed area shall not overlap the first. as well as the hydrogen concentration. Each material will have
The specimen preparation procedure in 9.1.1 must be started no a background current density (see 8.3) as a result of passivation
more than 10 min after completion of the previous measure- reactions. A measurement higher than background indicates the
ment taken in 9.3.2. presence of hydrogen; higher current densities indicate higher
9.4.2 If a series of measurements are to be made during the hydrogen concentrations. The higher the current density, the
day, alternate Ni/NiO electrodes and gaskets must be used. more chance there will be for hydrogen embrittlement (see 4.1
Allow at least 45 min between runs using the same ones. and 4.2).

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11.2 Irregular recorder tracings, Fig. 5, indicate scratches or 12. Report
pits, crevices, or gas bubbles. If the cell is constructed and 12.1 The report shall include the following:
filled properly, gas bubbles should not form. A light tap on the 12.1.1 The 30-min current reading for each measurement
cell should dislodge any bubbles. If, after doing this, the and the calculated specimen mean.
recorder trace is still poor, terminate the measurement, and 12.1.2 The area and the calculated specimen mean current
start a new one in accordance with 9.2. To prevent problems as density.
a result of deep scratches or pits, visually inspect the specimen 12.1.3 The type of specimen: coupon or part, part number,
before the measurement. Crevices can be a problem if the cell lot, steel grade, temper/condition, plating applied, and baking
is not tightened properly. Undertightening will allow the time and temperature.
solution to run under the gasket producing an enlarged contact 12.1.4 Any deviations from standard procedure, such as in
area and leading to crevice corrosion. Overtightening will surface preparation, delays in starting the measurement, or
cause the gasket to become deformed, thus changing the area. abnormal temperature.
Corrosion in a pit or crevice, or an enlarged contact area, will
all lead to excess measured current. If difficulties continue, 13. Precision and Bias
they are most probably a result of the gasket. Test the cell 13.1 Precision—Interlaboratory precision has not been de-
tightening procedure in accordance with 8.2. termined. Intralaboratory precision has been reported (2,3);
typical data are shown in Table 1 (2).
11.3 A high level of hydrogen is an indication of probable
hydrogen embrittlement problems. The absence, or a low level, TABLE 1 Hydrogen Measurements on Cadmium-Plated 300-M
of hydrogen does not, however, prove that hydrogen embrittle- Steel Coupons
ment has not occurred. It is possible that a high level of NOTE 1—The measurements were made by the same operator over a
hydrogen introduced during processing, such as pickling or period of two months. The 0.0005-in. (0.01-mm) thick bright cadmium
electroplating, may have caused local damage before diffusing plate was left on until the measurements were made.
out. Procedures, such as in Practices B183 and B242, must Baking Time, h Average Measurements,A Standard DeviationA
µA/cm2
therefore be adhered to.
0 0.60 0.076
11.4 Care must also be exercised in inferring hydrogen 48 0.45 0.086
72 0.42 0.073
levels over the whole part from limited measurements, espe- 96 0.38 0.036
cially when the part has quite variable geometries or possible A
The means and standard deviations were calculated from the specimen means
local metallurgical variations. For example, an electroplated, (two measurements each) using four specimens for each baking time.
massive part, having thin sections, may show a low hydrogen
level when measured on the thick parts; however, the thin
sections will have higher hydrogen concentrations because of 13.2 Bias—There is no need to determine bias in this test
higher surface-to-volume ratios (3). Thus, stresses at these method because the actual hydrogen concentration is not
areas would be more damaging than stresses on the bulk. determined; however, the measured current densities can be
related to relative hydrogen concentrations.
11.5 As this measurement is relatively rapid, it measures
hydrogen that diffuses easily. It is therefore probable that 14. Keywords
trapped hydrogen that is not easily released without stress, but 14.1 barnacle cell; current transients; diffusion; electro-
which could contribute to delayed failure, would not be chemical; electrodes; high strength steels; hydrogen contact;
detected. hydrogen embrittlement; mobile hydrogen

REFERENCES

(1) De Luccia, J. J., and Berman, D. A.,“ An Electrochemical Technique (4) Hay, M. G., Dautovich, D. P., and Dobson, W. P., “Electrochemical
to Measure Diffusible Hydrogen in Metals (Barnacle Electrode),” Monitoring of Carbon Steel Corrosion in Heavy Water Production,”
Electrochemical Corrosion Testing , ASTM STP 727, F. Mansfeld, and Materials Performance, June 1977, pp. 30–36.
U. Bertocci, Eds., 1981, pp. 256–273. (5) Agarwala, V. S., “A Probe for Monitoring Corrosion in Marine
(2) Berman, D. A., “The Effects of Baking and Stressing on the Hydrogen Environments,” Atmospheric Corrosion, W. H. Ailor, Ed., John Wiley,
Content of Cadmium—Plated High Strength Steels,” Materials 1982, p. 183–192.
Performance, November 1985, pp. 36–41. (6) Mansfeld, F., Jeanjaquet, S., and Roe, D. K., “Barnacle Electrode
(3) Berman, D. A., and Agarwala, V. S., “The Barnacle Electrode Method Measurement System for Hydrogen in Steels,” Materials
to Determine Diffusible Hydrogen in Steels,” Hydrogen Embrittle- Performance, February 1982, pp. 35 to 38.
ment: Prevention and Control, ASTM STP 962, L. Raymond, Ed.,
1987, pp. 98–104.

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