metals

Article
Glow Discharge Optical Emission Spectrometer
Calibration Using Hydrogenated Zr-2.5Nb Alloy
Standard Samples
Tatyana S. Priamushko, Andrey A. Mikhaylov, Maria N. Babikhina, Viktor N. Kudiiarov * ID
and
Roman S. Laptev ID
Division for Experimental Physics, School of Nuclear Science & Engineering, National Research Tomsk
Polytechnic University, Tomsk 634050, Russia; tatyana.pryamushko@gmail.com (T.S.P.);
useyourbrainagain@gmail.com (A.A.M.); m.babihina@mail.ru (M.N.B.); laptevrs@tpu.ru (R.S.L.)
* Correspondence: viktor.kudiiarov@gmail.com; Tel.: +7-913-870-0989




Received: 13 April 2018; Accepted: 20 May 2018; Published: 22 May 2018


Abstract: Currently, standard samples of hydrogen-metal systems meeting the requirements of glow
discharge optical emission spectrometers (GD-OES) are not available on the market. This article
describes the preparation of Zr-Nb-H standard samples and the calibration of GD-OES with the
usage of these samples. Samples of Zr-2.5Nb were chosen as the material for sample production.
The creation procedure includes five main steps: sample preparation (polishing to an average
roughness, Ra, of 0.04 m using sandpaper), annealing, hydrogenation, maintenance in an inert gas
atmosphere, and characterization of the samples. The absolute hydrogen concentration in the samples
was determined volumetrically and calculated from the weight change. The distribution of hydrogen
was studied using GD-OES Profiler 2 by Jobin Yvon Emission Horiba Group. As a result of this work,
calibration curves of Zr, H, Nb, O, and other elements were obtained. The calibration errors were in
the range of 1–5%.

Keywords: GD-OES; hydrogen; standard samples; zirconium alloy

1. Introduction
Zirconium and its alloys are well-known and established construction materials used in nuclear
reactors [1]. They are widely utilized due to their good mechanical properties at high temperatures and
their good resistance to corrosion [2]. Zirconium alloys are exploited in these aggressive environments.
This may cause changes in the structure due to the penetration of gases into the material. Many
macroscopic properties of metals and their alloys depend on hydrogen, which is a common impurity
found in structural materials after their usage [3–8]. Hydrogen can cause phase transformations
leading to hydride formation [9–16], interactions with structural defects modifying the plastic activity
of materials [17], the interplay with point defects provoking swelling [18–21], or so-called hydrogen
embrittlement. It makes the development of methods for the protection of zirconium alloys from
penetration of hydrogen significant. The main part of these studies is an elemental analysis of the
materials, which includes qualitative and quantitative analysis.
Unfortunately, quantitative analysis techniques of hydrogen are limited. Most of the techniques
capable of determining hydrogen concentrations need special facilities [22]. For that reason, glow
discharge optical emission spectrometry (GD-OES) has been considered a useful technique. GD-OES
is a popular method for routine elemental analysis of metals and alloys and depth profiling of
various coatings, with a typical depth ranging from nanometers to more than 100 micrometers [23,24].
The equipment’s small-volume vacuum chamber is a Grim-type glow discharge lamp, where the

Metals 2018, 8, 372; doi:10.3390/met8050372 www.mdpi.com/journal/metals

Metals 2018, 8, 372 2 of 9

sample is used as a cathode [25]. Ar, Ne, Kr, and their mixtures with each other or with reaction
gasses like O2 , N2 , and H2 are widely used as working gasses in GD-OES. The working gas is
injected into the small-volume vacuum chamber with a low pressure (few hundreds of Pa). A high
voltage (500–1000 V) is applied to the cathode, and glow discharge plasma is generated between the
electrodes [26]. Sample sputtering occurs; meanwhile, the characteristic emissions of the exited atoms
are generated. Due to emission wavelength division, it is possible to perform optical elemental analysis.
Compared to other technologies, the main advantage of this method is the high-speed analysis of
a sample, which depends on the material reaching 5 microns/min. At the same time, the advantages
of it include ease of use, fast sputtering rate, high depth resolution, and excellent sensitivity for low
concentrations, multi-element capability, good quantification, and high sample throughput [27–29].
However, for performing quantitative analysis of hydrogen by GD-OES, suitable certified
reference materials are not available. Thus, the aim of this work is to develop standard Zr-Nb-H
samples for calibration of GD-OES.
Usually Zr-1Nb and Zr-2.5Nb are used as construction materials in nuclear reactors in Russia.
Moreover, the bigger the concentration ranges of the impurities in the material, the higher the accuracy
of the analysis during the measurements in these ranges [29]. Thus, the usage of the Zr-2.5Nb alloy as a
material for the standard samples makes the calibration more universal in comparison with calibration
by use of Zr-1Nb samples.

2. Materials and Research Methods

2.1. Standard Samples Production

The Zr-2.5Nb samples with dimensions of 20 mm diameter and 2 mm thickness (elemental
composition is in Table 1) were polished to the average roughness (Ra) of 0.045 µm because the surface
condition has a strong influence on the penetration of hydrogen into the material. The GD-OES
technique is also very sensitive to the roughness of the surface of the analyzed specimen [23].
Roughness is a key factor in limiting the depth resolution of analysis and, for example, if the
roughness is similar to the thickness of the analyzed layer, severe degradation of depth resolution
occurs. Roughness causes the nonuniform removal of the material and modification of the surface
topography during the sputtering.

Table 1. Elemental composition of Zr-Nb alloys.

Element Content, Weight % Element Content, Weight % Element Content, Weight %

Zr Balance Cr 0.02 Mo 0.005
Nb(for Zr1Nb) 0.9–1.1 C 0.02 Pb 0.005
Nb(for Zr2.5Nb) 2.4–2.7 Ca 0.01 Ti 0.005
O 0.1 (max) Al 0.008 K 0.004
Fe 0.05 Ni 0.007 Cl 0.002
Hf 0.05 N 0.006 Mn 0.002
Si 0.02 Cu 0.005 Li 0.0008

The samples were annealed at the temperature of Ta = 580 ◦ C for ta = 180 min to remove the
internal stresses and structural defects. Hydrogenation was performed in hydrogen atmosphere at
the temperature of Th = 600 ◦ C and the pressure of Ph = 0.66 atm. The most common method for
studying hydrogen sorption by materials is Sievert’s method [30,31], in which hydrogen saturation
of the samples comes from gaseous atmosphere. Hydrogen saturation was carried out using an
Automated Complex Gas Reaction Controller (Advanced Materials Corporation, Pittsburgh, PA, USA)
using Sievert’s method [32]. The usability of the complex and the reliability of the results have been
previously checked on LaNi5 samples. After the saturation, in order to achieve a uniform distribution
of hydrogen by volume, the samples were maintained in an inert gas atmosphere at the temperature of
Tm = 600 ◦ C and the pressure of Pm = 0.66 atm for tm = 5 h, after that, the temperature decreased by
Metals 2018, 8, 372 3 of 9

2 ◦ C/min for 3 h. Different concentrations of hydrogen was achieved by variation in hydrogenation

time. To determine the concentrations, a melting method was used in an inert gas medium with the
registration of hydrogen in a special cell.

2.2. Standart Samples Characterization

The absolute hydrogen concentration in the samples was determined volumetrically [30,31],
calculated from the weight change and using the RHEN 602 hydrogen analyzer (LECO, Saint Joseph,
MI, USA). The determination of hydrogen distribution was carried out by the use of GD-OES.

2.3. Optimization and Calibration of GD-OES

Samples with the size of 20 × 20 × 1 mm were used for the selection of the optimal Zr-1Nb and
Zr-2.5Nb alloys sputtering parameters, as well as for the determination of the sputtering rate. For these
aims, a GD Profiler 2 (Jobin Yvon Emission Horiba Group, Longjumeau Cedex, France) was used.
The instrument is equipped with a standard GD source with an anode of 4 mm internal diameter.
Two optical spectrometers (poly- and monochromator) are used in Profiler 2. One of the
spectrometers is a 0.5 m Paschen-Runge polychromator with a concave grating of 2400 lines/mm.
The optical path of the spectrometer is nitrogen purged. The system is equipped with a Czerny–Turner
monochromator (0.64 m focal length, blazed planar holographic grating of 2400 lines/mm), which
allows the expansion of the instrument’s capabilities to any wavelength of the spectral range. Table 2
presents the monitored analytical emission lines. The samples were cooled at 10 ◦ C by a cold liquid
circulating between the sample and the RF power input.

Table 2. Analytical emission lines selected.

Element Wavelength, nm Element Wavelength, nm Element Wavelength, nm

H 121.574 Fe 271.445 Ti 365.355
O 130.492 Hf 286.641 Mo 386.416
Cl 134.730 Si 288.162 Al 396.157
N 149.268 Nb 316.345 Ca 422.679
C 156.149 Cu 324.759 Cr 425.439
Pb 220.357 Zr 339.203 Li 670.800
Mn 257.614 Ni 341.482 K 766.500

The developed samples were used for the GD-OES instrument’s calibration. The depth of the
craters was measured with the help of a T1000 profilometer (Hommel-Etamic, Jenoptik, Germany).
A three-dimensional non-contact profilometer MicroMeasure 3D Station (STIHL, Waiblingen, Germany)
was used to construct a 3D-image of the craters. The electrical parameters, e.g., plasma impedance,
effective power, etc., affecting the sputtering rate, were not monitored in this study since these need
the use of special equipment.

3. Results and Discussion

3.1. Sample Characterization

Table 3 represents the results of hydrogen concentrations determination. It is shown that
hydrogen concentrations determined by two different methods have a good correlation. Consequently,
the concentrations of hydrogen calculated from the weight change that have been confirmed by
measurement results using a hydrogen analyzer were chosen as the standard concentrations for the
calibration of GD-OES.
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Table 3. Hydrogen concentrations.

Table 3. Hydrogen concentrations.
Hydrogenation Time, Changing of Weight,
Sample Volumetrically, Weight %
min Weight %
Sample Hydrogenation Time, min Volumetrically, Weight % Changing of Weight, Weight %
Zr-2.5Nb-1 10 0.07 ± 0.01 0.08 ± 0.01
Zr-2.5Nb-1 10 0.07 ± 0.01 0.08 ± 0.01
Zr-2.5Nb-2
Zr-2.5Nb-2 13 13 0.10 ± 0.01
0.10 ± 0.01 0.12±± 0.01
0.12 0.01
Zr-2.5Nb-3
Zr-2.5Nb-3 17 17 0.19
0.19 ±
± 0.02
0.02 0.20±± 0.03
0.20 0.03
Zr-2.5Nb-4
Zr-2.5Nb-4 43 43 0.63
0.63 ±
± 0.03
0.03 0.64±± 0.05
0.64 0.05
Zr-2.5Nb-5 57 0.90 ± 0.07 1.00 ± 0.09
Zr-2.5Nb-5 57 0.90 ± 0.07 1.00 ± 0.09

3.2.3.2. Optimization
Optimization ofofGD-OES
GD-OES
ToTo selectthe
select theoptimal
optimal sputtering
sputteringparameters,
parameters, thethe
measurements
measurementswerewere
performed 14 times.
performed 14 The
times.
Thepressure was changed from 550 Pa to 800 Pa and the power of the discharge was changed from 30 W
pressure was changed from 550 Pa to 800 Pa and the power of the discharge was changed
to 50
from 30 W.
W toThe
50 selection was based
W. The selection wasonbased
the crater
on the shape.
craterPressure of 700 Paofand
shape. Pressure 700power
Pa andofpower
40 W ofwere
40 W
chosen
were as the
chosen optimal
as the parameters
optimal due to
parameters thetoflat
due thebottom without
flat bottom concaves
without and peaks
concaves and (Figure 1).
peaks (Figure 1).

Figure 1. 3D profile of the crater obtained by sputtering with the optimal parameters of 700 Pa and 40 W.
Figure 1. 3D profile of the crater obtained by sputtering with the optimal parameters of 700 Pa and 40 W.

Erosion rate was determined from the crater depth, with the average being 5 μm/min. The
Erosion
density rateZr-2.5Nb
of the was determined from
alloy is 6.57 the3crater
g/cm depth, with the
(by manufacturer). average
Relative being 5 µm/min.
sputtering The density
rate was calculated
3 (by manufacturer). Relative sputtering rate was calculated with the
with the use of the reference high steel alloy sample JK49, and it is 1.206. The “sputter
of the Zr-2.5Nb alloy is 6.57 g/cm
userate-corrected”
of the reference mode
highwas
steelchosen for the calibration
alloy sample JK49, and itinisthis work.
1.206. TheTo the bestrate-corrected”
“sputter of our knowledge,modethis
was
modefor
chosen is the
thecalibration
best calibration
in thismethod
work. To forthe
thebest
analysis
of our of the complex
knowledge, thisalloys
mode in a wide
is the best range of
calibration
concentrations.
method for the analysis of the complex alloys in a wide range of concentrations.

3.3.3.3. Calibration
Calibration of ofGD-OES
GD-OESwith
withthe
theUse
UseofofZr-2.5Nb
Zr-2.5Nb Samples
Samples
Most
Most ofof the
the elements’curves
elements’ curvesare arestraight
straight lines
lines because
because their
theirconcentrations
concentrationsare areidentical
identicalto to
thethe
standard
standard concentrationsininthe
concentrations thesamples.
samples.Figure
Figure 22 presents
presents the
thecalibration
calibrationcurves
curvesfor forallall
the samples
the samples of of
thethe following
following elements:
elements: C (156.149),
C (156.149), Cl (134.730),
Cl (134.730), Hf (286.641),
Hf (286.641), K (766.500),
K (766.500), Pb (220.357),
Pb (220.357), and Si
and Si (288.162).
(288.162).
Cc*q on the yCc*qaxis on therelative
is the y axis is the relative
sputtering rate.sputtering rate.sputtering
The relative The relative
rate,sputtering rate, i.e.,
i.e., the masses the
removed
masses removed per second, is an important parameter in the GD-OES method.
per second, is an important parameter in the GD-OES method. The straight lines for the relative The straight lines for
the relative sputtering rates of different elements means that the masses removed
sputtering rates of different elements means that the masses removed per second for every element with per second for
every element
different with different
concentrations concentrations
are constant. are constant.
It is very important It is very
for creating importantmethod
a calibration for creating
with higha
calibration method with high accuracy. It is shown that the intensity changes are
accuracy. It is shown that the intensity changes are negligible. The concentrations of the other elements negligible. The
concentrations of the other elements except Zr, O, Nb, and H determined in the calibration are
except Zr, O, Nb, and H determined in the calibration are similar to the announced concentrations.
similar to the announced concentrations.
The element contained in the material in the highest concentrations should have the highest errors
The element contained in the material in the highest concentrations should have the highest
in the calibration if the linear approximation is used. However, in analytical applications, empirical
errors in the calibration if the linear approximation is used. However, in analytical applications,
functions are used, established by the calibration, and are represented by a higher-order polynomial
empirical functions are used, established by the calibration, and are represented by a higher-order
instead of the direct proportionality [33]. In this case, a two-order polynomial function was used in
polynomial instead of the direct proportionality [33]. In this case, a two-order polynomial function was
theused
calibration of zirconium
in the calibration (Figure 3a).
of zirconium It is shown
(Figure 3a). It isthat the zirconium
shown concentration
that the zirconium in the samples
concentration in the
decreases with the increasing of the sample number due to increasing of the hydrogen concentration.
The sample named with the highest number (e.g., Zr-2.5Nb-5) has the highest concentration of
Metals 2018, 8, x FOR PEER REVIEW 5 of 9
Metals 2018, 8, x FOR PEER REVIEW 5 of 9
Metals 2018, 8, 372 5 of 9
samples decreases with the increasing of the sample number due to increasing of the hydrogen
samples decreases with the increasing of the sample number due to increasing of the hydrogen
concentration. The sample named with the highest number (e.g., Zr-2.5Nb-5) has the highest
concentration. The
3). sample named with the highest number (e.g., Zr-2.5Nb-5) hashigh
the accuracy.
highest
concentration
hydrogen of hydrogen
(Table (Table 3). The
The polynomial polynomial
function lies onfunction
the lies on thepoints
experimental experimental
with points with
concentration of hydrogen (Table 3). The polynomial function lies on the experimental points with
highexpected
The accuracy.points
The expected
have thepoints
same have the same
behavior. The behavior.
determinedTheconcentrations
determined concentrations of Zr are
of Zr are presented in
high accuracy. The expected points have the same behavior. The determined concentrations of Zr are
presented
Table in Table
4 (in weight %).4 The
(in error
weight %).Zr-calibration
of the The error ofhasthe Zr-calibration
been has been determined
determined automatically and it is
presented in 1%.Table 4 (in weight %). The error of the Zr-calibration has been determined
automatically and it is approximately 1%.
approximately
automatically and it is approximately 1%.

Figure 2.2.Calibration
Figure2. curves
Calibration curves of
curves of carbon
of carbon (156.149),
carbon (156.149), chlorine
(156.149), chlorine (134.730), hafnium
chlorine (134.730),
(134.730), hafnium (286.641), potassium
potassium
Figure Calibration hafnium (286.641),
(286.641), potassium
(766.500), lead
(766.500),lead (220.357),
lead(220.357), and
(220.357),and silicon
andsilicon (288.162).
silicon(288.162).
(288.162).
(766.500),

Figure
Figure 3a 3a presents
presents the
the calibration
calibration curve
curve of oxygen. The concentration
concentration of of oxygen
oxygen isis notnot
Figure
accurately 3a presents
defined by the
the calibration
manufacturer
accurately defined by the manufacturer (Tablecurve of
(Table oxygen.
1) and The
it is concentration
0.1 weight % of oxygen
(max). is
Herein, not accurately
the
weight % (max). Herein, the highest highest
defined
value
value wasby the
was manufacturer
chosen
chosen as
as the (Table 1) and
the theoretical
theoretical it is 0.1 weight
concentration
concentration % (max).
to make Herein,
the range
the range ofthe
of thehighest
the value was
O-concentration
O-concentration
chosen as the
determination theoretical
determinationwider.
wider. The concentration
The theoretical to make
theoretical concentration the range of
concentration is used for the the O-concentration
the calculation
calculation ofof the determination
the experimental
experimental
wider. The theoretical
concentration. The concentration
experimental is
points
concentration. The experimental points don’t used
don’tfor the calculation
correlate with of
the the experimental
the theoretical points, as
theoretical points, concentration.
as expected
expected
The experimental
becauseofofthe
because points
thesimilar don’t
similartheoretical correlate with
theoretical concentrations the theoretical points,
concentrations of oxygen for each as expected
each sample because
sample (Figure
(Figure3a). of
3a).The
Thetheerror
similar
errorofof
theO-calibration
the O-calibration isis approximately
theoretical approximately 3%.
concentrations of oxygen 3%. Table
for Table 4 represents the results
each sample (Figure results of
3a). The of calibration
calibration in
error of the in weight
weight%.
O-calibration is
%.
Takinginto
Taking intoaccount
approximately account these
3%. Table
these results, we
4 results,
represents wethe
canresults
can conclude
conclude that the determination
of calibration in weight %. of
determination oxygen
Taking
of into
oxygen concentrations
account these
concentrations
wascarried
was carriedout
results, we outsuccessfully.
can successfully.
conclude that the determination of oxygen concentrations was carried out successfully.

(a) (b)
(a) (b)
Figure 3. Calibration curves of (a) oxygen (130.492) and (b) niobium (316.345).
Figure 3.
Figure 3. Calibration
Calibration curves of (a)
curves of oxygen (130.492)
(a) oxygen (130.492) and
and (b)
(b) niobium
niobium (316.345).
(316.345).

Figure 3b shows the results of niobium calibration. It is the same task as the oxygen calibration.
Figure 3b
3b shows
shows the
the results
results of
of niobium
niobium calibration.
calibration. It
It is
is the same task
taskofas the oxygen calibration.
TheFigure
Nb-concentration range is 2.3–2.7 weight % (Table 1). Herein, thethe value
same 2.5the
as weight
oxygen% was chosen
calibration.
The Nb-concentration range is 2.3–2.7 weight % (Table 1). Herein, the value of 2.5 weight % was chosen
chosen
as a theoretical concentration to make a range of the concentration determination more accurate. It is
The Nb-concentration range is 2.3–2.7 weight % (Table 1). Herein, the value of 2.5 weight % was
as a theoretical
asshown concentration to make a range of the concentration determination more accurate. It is
that niobium
a theoretical concentration
concentration to make in the samples
a range decreases with
of the concentration the increasing
determination more ofaccurate.
the sampleIt is
shown that
shown thatniobium
niobiumconcentration
concentration in the
in the samples
samples decreases
decreases with
with the the increasing
increasing of the number,
of the sample sample
Metals 2018, 8, 372 6 of 9
Metals 2018, 8, x FOR PEER REVIEW 6 of 9

number,
as as for zirconium
for zirconium (Figure
(Figure 4a). 4a). Experimental
Experimental points lie points
withinliethewithin the calibration
calibration curve with curve
highwith high
accuracy.
accuracy. concentrations
Niobium Niobium concentrations
determined determined
as weight % as are weight
presented % inareTable
presented in concentrations
4. All the Table 4. All the lie
concentrations
within the rangelieprovided
within theby range provided by(Table
the manufacturer the manufacturer
1). (Table 1).
The calibration
The calibration curve
curve is
is aa basis
basis for
for the
the quantification.
quantification. IfIf aa sample
sample with
with the
the known
known concentration
concentration
and sputtering
and sputtering raterate deviates
deviates from
from the
the calibration
calibration curve,
curve, the
the quantification
quantification ofof concentration
concentration and and
thickness will
thickness will be
be wrong
wrong [33].
[33]. The
The calibration
calibration curve
curve ofof hydrogen
hydrogen is is represented
represented in in Figure
Figure 4b.
4b. It
It isis
shown that
shown that the
the expected
expectedand
andthe theexperimental
experimentalpoints
pointsare
arewell
wellcorrelated.
correlated.Results
Resultspresented
presentedininTable
Table 4
4 prove the high accuracy of this calibration. Hydrogen is the lightest element and
prove the high accuracy of this calibration. Hydrogen is the lightest element and due to this fact, due to this fact, its
quantification
its quantification in in
metals is is
metals a very
a verydifficult
difficulttask.
task.The
Theerror
errorofofthe
the H-calibration
H-calibration waswas calculated
calculated toto bebe
approximately 5%,
approximately 5%, demonstrating
demonstrating the the high-resolution
high-resolutioncapability
capabilityof ofthe
thecalibration.
calibration.

(a) (b)
Figure 4. Calibration curves of (a) zirconium (339.203) and (b) hydrogen (121.574).
Figure 4. Calibration curves of (a) zirconium (339.203) and (b) hydrogen (121.574).

Table 4. Results of the calibration with the usage of Zr-2.5Nb samples: C1—concentration which was
Table 4. Results of the calibration with the usage of Zr-2.5Nb samples: C1—concentration which
used as average theoretical value, C2—determined concentration during the calibration, % wt—% in
was used as average theoretical value, C2—determined concentration during the calibration, % wt—
weight.
% in weight.
Sample Concentration Zr Nb O H
Sample C1, weight %
Concentration 97.100
Zr 2.500
Nb 0.100
O 0.080
H
Zr-2.5Nb-1
C2,weight
C1, weight%% 96.970
97.100 2.689
2.500 0.100
0.100 0.106
0.080
Zr-2.5Nb-1
C1,weight
C2, weight%% 97.060
96.970 2.500
2.689 0.100
0.100 0.120
0.106
Zr-2.5Nb-2
C2, weight%%
C1, weight 97.160
97.060 2.606
2.500 0.098
0.100 0.106
0.120
Zr-2.5Nb-2 C1, weight%%
C2, weight 96.990
97.160 2.500
2.606 0.100
0.098 0.200
0.106
Zr-2.5Nb-3
C2, weight % 97.130 2.597 0.108 0.217
C1, weight % 96.990 2.500 0.100 0.200
Zr-2.5Nb-3 C1,weight
weight%% 96.550 2.500 0.100 0.640
Zr-2.5Nb-4 C2, 97.130 2.597 0.108 0.217
C2, weight % 96.480 2.324 0.092 0.554
C1, weight % 96.550 2.500 0.100 0.640
Zr-2.5Nb-4 C1, weight % 96.400 2.500 0.100 1.000
Zr-2.5Nb-5 C2, weight % 96.480 2.324 0.092 0.554
C2, weight % 96.817 2.124 0.103 0.956
C1, weight % 96.400 2.500 0.100 1.000
Zr-2.5Nb-5
C2, weight % 96.817 2.124 0.103 0.956
3.4. Measurements of the Other Samples in the Calibration
The application
3.4. Measurements of Other
of the the performed
Samples incalibration is the quantitative depth-profile measurements of
the Calibration
Zr-Nb-H samples with an unknown concentration of hydrogen. To check the correctness and the
The application
accuracy of the performed
of the calibration, calibration
two different samplesisoftheZr2.5Nb
quantitative
(afterdepth-profile
annealing) and measurements of
Zr2.5Nb (with
Zr-Nb-H samples with an unknown concentration of
hydrogen concentration approximately 0.2 weight %) were chosen.hydrogen. To check the correctness and the
accuracy of 5a
Figure thepresents
calibration, two different
the depth profile ofsamples of Zr-2.5Nb
the initial Zr2.5Nb (after annealing)
alloy sample afterand
the Zr2.5Nb (with
annealing. The
hydrogen concentration approximately 0.2 weight %) were chosen.
concentration of Zr is approximately 97 weight %, Nb-2.5 weight %, O-0.1 weight %. Hydrogen is
Figureonly
observed 5a presents the depth layer
in the pre-surface profile(approximately
of the initial Zr-2.5Nb
500 nm),alloy
then sample after the annealing.
its concentration decreases
The concentration of Zr is approximately 97 weight %, Nb-2.5 weight %, O-0.1 weight %.
extremely to 0 weight %. Correct depth calculation is one of the main indications of the calibration Hydrogen
is observed
ability. only inofthe
The depth pre-surface
crater layer
calculated (approximately
during the calibration500was
nm), then its concentration
compared with the depthdecreases
obtained
by the measurements by profilometer. The difference is approximately 0.3 μm.
Metals 2018, 8, 372 7 of 9

extremely to 0 weight %. Correct depth calculation is one of the main indications of the calibration
Metals 2018, 8, x FOR PEER REVIEW 7 of 9
ability. The depth of crater calculated during the calibration was compared with the depth obtained by
Figure 5b shows
the measurements by the depth profile
profilometer. Theofdifference
the Zr-1Nb alloy sample after
is approximately 0.3 annealing,
µm. hydrogenation, and
maintenance in an inert gas atmosphere for 5 h. The concentration of hydrogen, as received fromand
Figure 5b shows the depth profile of the Zr-1Nb alloy sample after annealing, hydrogenation, the
quantificationinby
maintenance anGD-OES, provides well-fitted
inert gas atmosphere results.
for 5 h. The Zirconiumofconcentration
concentration hydrogen, as is ≈ 98 weight
received %,
from the
niobium concentration is uniform, 1.3 weight %. Oxygen concentration is lower than 0.1 weight %. The
quantification by GD-OES, provides well-fitted results. Zirconium concentration is ≈ 98 weight %,
differenceconcentration
niobium between the calculated and1.3
is uniform, measured
weight %. crater depths
Oxygen is approximately
concentration 0.5 μm.
is lower than 0.1 weight %.
The difference between the calculated and measured crater depths is approximately 0.5 µm.

(a) (b)

Figure 5. The depth profile of (a) Zr-2.5Nb alloy after annealing without hydrogenation and (b)
Figure 5. The depth profile of (a) Zr-2.5Nb alloy after annealing without hydrogenation and (b) Zr-1Nb
Zr-1Nb alloy after annealing, hydrogenation, and maintenance in inert gas atmosphere.
alloy after annealing, hydrogenation, and maintenance in inert gas atmosphere.

4. Summary
4. Summary
In this work, a method for production of Zr-Nb-H calibration samples was performed. Samples
In this work, a method for production of Zr-Nb-H calibration samples was performed. Samples
of Zr-2.5Nb alloy were chosen for the research. The annealing, hydrogenation, and maintaining were
of Zr-2.5Nb alloy were chosen for the research. The annealing, hydrogenation, and maintaining
performed with the usage of Automated Complex Gas Reaction Controller. The temperature of
were performed with the usage of Automated Complex Gas Reaction Controller. The temperature of
hydrogenation was T = 600 °С and the pressure was p = 0.66 MPa, the temperature at which it was
hydrogenation was T = 600 ◦ C and the pressure was p = 0.66 MPa, the temperature at which it was
maintained was T = 600 °С at the same pressure. Hydrogen distribution was studied by GD-OES; the
maintained was T = 600 ◦ C at the same pressure. Hydrogen distribution was studied by GD-OES;
absolute hydrogen concentrations were determined volumetrically, calculated from the weight
the absolute hydrogen concentrations were determined volumetrically, calculated from the weight
change and using the hydrogen analyzer.
change and using the hydrogen analyzer.
The optimization and calibration of GD-OES were carried out; the sputtering rate of Zr-2.5Nb
The optimization and calibration of GD-OES were carried out; the sputtering rate of Zr-2.5Nb
alloy was determined. The erosion rate was determined from the crater depth, the average is 5
alloy was determined. The erosion rate3 was determined from the crater depth, the average is 5 µm/min.
μm/min. The density is 6.57 g/cm for Zr-2.5Nb, provided by the manufacturer. The relative
The density is 6.57 g/cm3 for Zr-2.5Nb, provided by the manufacturer. The relative sputtering rate
sputtering rate was calculated with the use of the reference high steel alloy sample JK49, and it is
was calculated with the use of the reference high steel alloy sample JK49, and it is 1.206. The “sputter
1.206. The “sputter rate-corrected” mode was chosen for the calibration in this work. Thus, the result
rate-corrected” mode was chosen for the calibration in this work. Thus, the result of this work is
of this work is a set of standard Zr-Nb-H samples. Hydrogen concentrations are approximately in
a set of standard Zr-Nb-H samples. Hydrogen concentrations are approximately in the range of
the range of 0.1–1.0 weight %.
0.1–1.0 weight %.
In the present work, we increased the range of the investigated concentrations, took into
In the present work, we increased the range of the investigated concentrations, took into account
account the sputtering rate of the material, and achieved an increase in the accuracy of calibration
the sputtering rate of the material, and achieved an increase in the accuracy of calibration due to
due to an increase in the content of niobium in the material in comparison with our previous work
an increase in the content of niobium in the material in comparison with our previous work [24].
[24]. An increase in the content of niobium in the material leads to a more accurate determination of
An increase in the content of niobium in the material leads to a more accurate determination of its
its concentration [29], and as a result, a higher precision of the entire experiment. It is now possible
concentration [29], and as a result, a higher precision of the entire experiment. It is now possible to
to investigate hydrogen distribution with high accuracy in zirconium materials of nuclear reactors
investigate hydrogen distribution with high accuracy in zirconium materials of nuclear reactors after
after their operation, or after experiments that simulate operating conditions using the developed
their operation, or after experiments that simulate operating conditions using the developed technique.
technique. This is especially important for the problem of hydrogen embrittlement and hydride rim
This is especially important for the problem of hydrogen embrittlement and hydride rim formation in
formation in zirconium claddings [14,15].
zirconium claddings [14,15].
Author Contributions: T.S.P. and A.A.M. carried out calibration of GD-OES, analyzed the results, and prepared
the paper. M.N.B. performed sample preparation and hydrogen concentration determination. V.N.K.
performed hydrogenation of samples, revised the manuscript, and directed the work. R.S.L. carried out testing
of calibration samples and analyzed the results.

Funding: This research received no external funding.

Metals 2018, 8, 372 8 of 9

Author Contributions: T.S.P. and A.A.M. carried out calibration of GD-OES, analyzed the results, and prepared
the paper. M.N.B. performed sample preparation and hydrogen concentration determination. V.N.K. performed
hydrogenation of samples, revised the manuscript, and directed the work. R.S.L. carried out testing of calibration
samples and analyzed the results.
Funding: This research received no external funding.
Acknowledgments: The research is carried out within the framework of the grant of the Program for Enhancing
Competitiveness of Tomsk Polytechnic University.
Conflicts of Interest: The authors declare no conflict of interest.

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