Polymer Testing 27 (2008) 705–710

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Analysis Method

Classification of polymers by determining of C1:C2:CN:H:N:O ratios by

laser-induced plasma spectroscopy (LIPS)
Jesús Anzano a, *, Roberto-Jesús Lasheras a, Beatriz Bonilla a, Justiniano Casas b
a
Laser Laboratory, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, Pedro Cerbuna #12, 50009 Zaragoza, Spain
b
Department of Condensed Matter Physics, University of Zaragoza, Pedro Cerbuna #12, 50009 Zaragoza, Spain

a r t i c l e i n f o a b s t r a c t

Article history: In the recycling of post-consumer plastic waste there is a pressing need for rapid, on-line
Received 25 March 2008 or at-line measurement technologies for simple identification of materials. The goal of this
Accepted 6 May 2008 work was instant identification of post-consumer plastics by laser-induced plasma spec-
trometry (LIPS). These polymers are often polyethylene terephthalate (PET), polyolefins
(polyethylene and polypropylene), poly(vinyl chloride) (PVC) and polystyrene (PS). A
Keywords:
new approach for the determination of major elemental ratios in organic compounds
Laser-induced plasma spectroscopy
such as polymers by using laser-induced plasma spectroscopy (LIPS) was investigated. In
Polymers
Classification previous works, we have shown that simple statistical correlation methods, such as linear
Ratios and rank correlations, can be successfully applied for identification of these materials. The
C2 Swan system (516 nm), the CN band (388 nm), the carbon (247.9 nm), hydrogen
(656.3 nm), oxygen (777.2 nm) and nitrogen (746.8 nm) emission intensity ratios were
used to identify the plastics. The most important ratios were C2/C1 and H/C1.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction different plastics. Raman spectroscopy has also been evalu-

Laser-induced plasma spectroscopy (LIPS) has been
used for industrial [1–5], biomedical [6–9], archeological
[10–18], geological [19–21] and environmental [22–26]
applications since the first publication in 1962 [27]. LIPS
has been used to identify polymers by different strategies:
(i) correlating the LIPS spectrum of the unknown with
library spectra [28,29] and (ii) using artificial neural net-
works [30]. The parametric and nonparametric correlation
method involves studying a lot of emission lines and
molecular bands. However, the methods by determining
ratios consist almost exclusively of a few lines and bands.
Such a method has been used before, giving excellent
results [31–36].
Other analytical techniques, such as Raman, infrared and
near infrared spectroscopy, are used for the identification of
* Corresponding author. Tel.: þ34 976762684; fax: þ34 976761292.
E-mail addresses: janzano@unizar.es, jesusanzano@gmail.com
(J. Anzano).
ated for discrimination between plastics. Raman spectra
provide structural fingerprint information that can be in-
vestigated for uniquely identifying plastics. Thus, the
potential of Raman spectroscopy for computerized
classification of common post-consumer plastics has been
demonstrated [37].
Infrared spectroscopy is one of the most important tech-
niques to identify plastics and has been subject to great de-
velopment [38–40]. In some cases, LIPS can be used to
complement NIR spectroscopy, which can also be applied
for the identification of polymer, as mentioned previously.
However, it is not suitable for dark-coloured samples.
This investigation group has carried out studies on
recycled plastic materials identification using a compact
Nd:YAG laser [28,29]. This method has been developed
for instant reliable classification (90–99%) of different
groups of plastic materials by means of statistical
correlation analysis.
Although a limitation exists for identification because of
the loss of molecular information in the plasma, the

0142-9418/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2008.05.012
706 J. Anzano et al. / Polymer Testing 27 (2008) 705–710
technique has excellent potential for on-line, real-time
analysis of recycled materials, which is really of interest
in order to obtain plastics separation faster and more effec-
tively. A Nd:YAG laser has been used for other applications
due to its simplicity, easy operation, high efficiency and low
cost. Despite all works and publications on LIPS that have
appeared in recent years, the laser plasma can offer new
advantages for plastics identification and separation in ac-
cordance with new exigencies of polymer industry and
science.
In previous papers about plastic [28] and geological ma-
terials [29], we have shown that simple statistical correla-
tion methods, such as linear and rank correlations, can be
successfully applied for identification of materials. A com-
pact LIP spectrometer was used for instant identification
of materials. Spectra were collected with a compact dual
channel fibre optic spectrometer and monitored either in
a 230–310 nm spectral window for geological material or
a 200–800 nm spectral window for plastic material. Both
studies were carried out applying parametric (linear) and
nonparametric (rank) correlation methods for identifica-
tion of compounds; and a nearly 100% reliable identifica-
tion was achieved.
In this study, the objective is to identify plastic materials
by determining the intensity ratios from elemental lines
and molecular bands. Measurements are made of the ratios
of several elements and molecular species, such as C1, H, N,
O, C2 system (Swan bands) and CN.
Molecular materials like plastics are almost entirely at-
omized when exposed to intense laser radiation. This im-
plies that limitations exist in application of LIPS for
identification of polymers because of the loss of molecular
information in the plasma [29]. In the present work, peak
ratio analysis in combination with analysis of molecular
bands was used for the identification of energetic materials.
The intensity ratio is related to the difference between the
upper energy levels of the lines and is also proportional to
the ratio of Boltzmann factors, becoming independent of
the ablated mass [41]. Therefore, it is expected to yield
better results than the single peak intensity alone.
Fig. 1. Experimental setup.
Nowadays, the identification of plastic materials in the
recycling industry is an important need because of the in-
crease of plastic waste. Hence, the compounds chosen for
study were commercial plastics.
In this study, the emission lines chosen for C, H, O and N
are 247.9 nm, 656.3 nm, 777.2 nm (triplet) and 746.8 nm,
respectively, and the molecular bands for C2 and CN are
516 and 388 nm, respectively.
2. Experimental
2.1. Instrumental setup
The instrumentation used consisted of a Nd:YAG laser,
a xyz stage carrying the sample (Standa 011957), a spectro-
graph and an intensified charge coupled device (ICCD) de-
tector. A diagram of this instrumentation is shown in Fig. 1.
A Nd:YAG laser (Brilliant Quantel, Q-Switched) with
a 115 mJ laser pulse energy at the second harmonic of
532 nm, a 4.4 ns pulse duration and 0.7 Hz repetition fre-
quency was used with a 90 mm focal length lens. The crater
diameter was 0.4 mm. The plasma light was collected and
transported to the spectrograph by lens and optical fibre
(fused silica, 50 mm core diameter). An external collector/
collimator was used as a collector lens, its position being
adjusted at 200 mm by a diode laser (Andor, HE-OPI-
0009). An Echelle spectrograph (Andor Mechelle ME5000,
focal length 195 mm, F/7, l/Dl 5000, spectral range from
200 to 975 nm) was coupled to an ICCD detector (Andor
iStar DH734, 1024  1024 pixels, 13.6  13.6 mm2/pixel,
18 mm diameter intensifier and the exposure time was
0.011 s). This system was calibrated by a Hg:Ar lamp (Ocean
Optics, HG-1, Hg–Ar lines 253–922 nm). The MCP gain was
fixed at 180. A measurement gate delay time of 1 ms and an
integration time of 1.5 ms were used.
2.2. Samples and sample preparation
Little sample preparation was necessary. This results in
increased throughput, greater convenience and fewer
 J. Anzano et al. / Polymer Testing 27 (2008) 705–710
opportunities for contamination to occur. The polymers
studied were: polyethylene terephthalate (PET), polyethyl-
ene (PE), high-density polyethylene (HDPE), low-density
polyethylene (LDPE), polypropylene (PP), polystyrene (PS)
and poly(vinyl chloride) (PVC).
Their formula, chemical structure and theoretical ratios
are shown in Table 1. A small piece of plastic (approxi-
mately 3  3 cm) was placed on double-sided tape stuck
to a glass slide. The piece of plastic must be completely
stuck to the slide in order to avoid air between them. Three
determinations were carried out for each sample. Each de-
termination is the average of ten shots and the discrep-
ancies were evaluated by a simple Grubbs test (p ¼ 0.05).

This test is shown in Eq. (1), where Xi is the value studied,
X is the average and s is the standard deviation.
707
deviation and RSD %, with all ratios checked by a simple
Grubbs test.
3. Results and discussion
3.1. Choice of analytical bounds and lines
The C2 Swan system and the CN band, as well as the car-
bon, hydrogen, oxygen and nitrogen, emission intensity ra-
tios were the necessary parameters to identify organic
compounds. Oxygen, nitrogen and hydrogen emission lines
and a number of molecular bands are used for this task. The
analysis of molecular bands [42,43] is focused on the detec-
tion of CN molecular violet bands at 386.17 nm, 387.14 nm
and 388.34 nm, and C2 carbon Swan bands at 516.52 nm.
The intensity of the Swan system is proportional to the con-
  
X LX  centration of the carbon dimer in the excited state, while
i
G[ (1) the CN bands’ emission could also be due to CN generation
s
in the ambient air. Hence, only the measurement of the C2
A simple program (Fig. 2) was designed for treatment of bands is reliable for analysis in the open atmosphere [35].
data. This application acquires the element signal and the The emission lines selected were: carbon at 247.9 nm,
maximum signal for molecular bands. Also it calculates au- hydrogen at 656.3 nm, nitrogen at 746.8 nm and oxygen
tomatically ratios, their averages of ten shots, the standard at 777.2 nm. The molecular bands selected were: CN at

Table 1
Polymers used and their theory ratios

Compound Molecular formula Chemical structure Ratioa H/C Ratiob C2/C1

O O

Polyethylene terephthalate, PET (C10H10O4)n * O CH2 CH2 O * 0.8 1

n

* CH2 CH2 *
Polyethylene, PE (C2H4)n 2 1.5
n

Cl H

* C C *
Poly(vinyl chloride), PVC (C2H3Cl)n n 1.5 1.5

H H

CH3

Polypropylene, PP (C3H6)n * CH CH2 * 2 1.33

n

* CH CH2 *
n

Polystyrene, PS (C8H8)n 1 1.25

a
Atomc ratio takes from molecular formula of her monomer.
b
Ratio C2/C1 ¼ (C–C and C]C) bounds/C atoms.
708 J. Anzano et al. / Polymer Testing 27 (2008) 705–710

DERMINATION OF ORGANIC COMPOUND RATIOS IN LASER-INDUCED PLASMA SPECTROSCOPY

Shot 1 Shot 2 Shot 3 Shot 4 Shot 5 Shot 6 Shot 7 Shot 8 Shot 9 Shot 10
Signal C I 247
Signal H656
Signal 0777
Signal N 744
Signal C II 516
Signal CN 388
Signal Cl

RATIOS
H/C
O/N
C II/C I
CN / C I
H / C II

Test Grubbs
H/C
O/N
C II/C I
CN / C I
H / C II
Valor de G tab (n=¿?, p=0,05)

Average H/C Average C II/C I Average H/C II

s H/C s C II/C I s CH/C II
% rsd % rsd % rsd

Average O/N Average CN/C I

s O/N s CN/C I
% rsd % rsd

Fig. 2. Automatic data treatment.

388 nm and C2 at 516 nm. These are the most intense lines
covered by our spectrometer and; in addition, these lines
are free from spectral interference. The Echelle spectro-
graph allowed us to obtain the signal ratios free of sample
matrix, laser and detector fluctuations, because it is able to
use a wide spectral window (from 200 to 975 nm) with
very high resolution (0.1 Å), detecting simultaneously all
elements and bands without overlapping.
Under our experimental conditions, atmospheric nitro-
gen and oxygen influence the spectra. Therefore, nitrogen
and oxygen signals appear in compounds without these el-
ements and, similarly, it occurs with the CN band. A better
approach would be to use an inert atmosphere, for exam-
ple, helium or argon. However, our objective is to analyse
polymer in recycling industrial conditions where a helium
or argon atmosphere is not possible.

20000
OI

15000
Intensity (Counts)

HI

10000

NI

5000
Swan bands Na I NI
OI
CN
CI

0
200 400 600 800 1000
wavelength (nm)

Fig. 3. Polyethylene terephthalate spectrum.

 J. Anzano et al. / Polymer Testing 27 (2008) 705–710 709

3.2. Ratios C1:C2:CN:H:N:O

The ratios were calculated by application of software

(Fig. 2). The spectral data were taken, outlier values elimi-
nated and the average ratios and RSD % of C1:C2:CN:H:N:O
calculated.
In organic compounds like polymers, the number of
possible ratios that could be used to identify them, are rel-
atively few. Characterisation of organic compounds using
LIPS requires careful data processing due to their similar
compositions. These ratios were: (i) H/C1 ratio, this is the
most important ratio for identifying [31] and differentiat-
ing [35] organic compounds; (ii) O/N ratio, under atmo-
spheric conditions if the compounds studied have no
nitrogen and oxygen then it will be constant. In this study
only the polyethylene terephthalate has oxygen; (iii) C2/
C1 ratio, which relates the carbon–carbon bonds and num-
ber of carbon atoms. Other ratios studied, less important,
are: CN/C1 and H/C2.
All organic compound LIPS spectra are similar. However,
relative differences in intensity are observed, due to stoi-
chiometric differences. A single shot LIP spectrum of poly-
ethylene terephthalate is shown in Fig. 3. In this spectrum,
the following emission lines can be observed: calcium at
393.4 and 396.9 nm, carbon at 247.9 nm, hydrogen at
656.5 nm, nitrogen at 742.6, 744.4, 747.1, 819.0, 821.8 and
824.5 nm, sodium at 589.1 and 589.6 nm, and oxygen at
777.4 (triplet) and 844.8 nm. The calcium emission might
be present as a result of polymer processing, therefore it
is considered a contamination. A chlorine signal appears
for the PVC at 837.8 nm. This weak signal is the most impor-
tant because it differentiates PVC from other materials.
The determinate ratios for the polymers studied are
shown in Table 2. The best RSD % results were obtained in
the H/C1, O/N and C2/C1 ratios. The worst RSD % were the
CN:O:N which did not contribute to the identification of
organic compounds.
3.3. Classification of polymers
Some relations between theoretical atomic ratios of
monomers and the signal ratios were studied by calibration
curves. The first calibration curve was for H/C1, which is the
most important because most compounds studied only
have hydrogen and carbon atoms. In Fig. 4, calibration
curve for H/C1 is given. The polyethylene ratio value is the
average of all of them (PE, LDPE and HDPE); the RSD of
these values was 2.4%. The PP ratio value was different to
the PE value, although they have the same atomic ratio
from molecular formula. However, a t-test (p ¼ 0.05) was
Fig. 4. Calibration curve of signal intensity ratios of H/C.
applied and significant differences were not observed for
different polypropylene (PP1, PP2 and PP3) and polyethyl-
ene samples (PE, HDPE and LDPE). Therefore, the H/C1 ratio
did not differentiate between polyethylene and polypropyl-
ene, it only classified them as polyolefin.
The C2/C1 signal ratio was used for the next calibration
curve. This signal ratio and the number of carbon–carbon
bonds/number of carbon atoms in the monomer were re-
lated; one C]C bond was counted as one C–C bond. The
calibration curve for C2/C1 is given in Fig. 5. Polypropylene
and polyethylene signal ratios were the same, although
their theoretical ratios are different. Therefore, the polyeth-
ylene was not used in the calibration. However, the C2/C1
ratio allowed identification of compounds such as polyeth-
ylene terephthalate, polyolefins, poly(vinyl chloride) and
polystyrene.
The ratios (H/C1 and C2/C1) allowed classification of the
different plastic materials, although they did not differenti-
ate between polyethylene and polypropylene. These were
identified only as polyolefin by this method.
The O/N signal ratio was the same for all compounds,
which may be due to the experimental conditions. The
other ratios (CN/C1 and H/C2) did not give useful results.
4. Conclusions
A LIPS system has been developed and optimised for in-
stant reliable classification of different groups of plastic
materials by using ratio analysis. A software application
was developed for data processing. In this work, signal

Table 2
Summary of the results obtained in the characterisation of plastics using ratios

PS PP 1 PP 2 PP 3 PE LDPE HDPE PET PVC

H/C1 5.14 (2.2) 7.8 (4.2) 11.9 (14.5) 8.5 (13.3) 11.46 (5.7) 10.92 (13.7) 11.2 (4.2) 4.47 (10.7) 7.4 (4.9)
O/N 3.75 (10.7) 3.2 (6.2) 3.2 (1.8) 3.4 (9.1) 3.02 (8.0) 3.05 (6.6) 3.49 (2.9) 3.69 (2.0) 3.31 (7.8)
C2/C1 1.27 (2.3) 1.1 (19.1) 1.5 (12.7) 1.6 (14.1) 1.32 (0) 1.67 (13.1) 1.35 (6.3) 1.01 (9.9) 1.87 (16.4)
CN/C1 1.38 (4.6) 1.5 (13.2) 1.5 (26.6) 1.3 (17.8) 1.23 (5.7) 1.43 (8.5) 1.05 (5.8) 1.23 (12.7) 2.22 (43.4)
H/C2 4.81 (2.5) 7.5 (20.1) 8.1 (2.1) 5.6 (6.3) 8.99 (3.8) 6.78 (4.2) 8.53 (3.3) 4.53 (10.2) 4.37 (11.3)

(RSD %).
710 J. Anzano et al. / Polymer Testing 27 (2008) 705–710
Fig. 5. Calibration curve of signal intensity ratios of C2/C1.
ratios of C:C2:CN:H:N:O of plastics were determined under
atmospheric conditions. The most important ratios were H/
C1 and C2/C1. Polymer materials can be classified according
to their signal ratios as polyethylene terephthalate (PET),
polyolefins (polyethylene and polypropylene), poly(vinyl
chloride) (PVC) and polystyrene (PS). The polyolefin group
cannot be differentiated into individual materials; there-
fore they can only be identified as polyolefins. The tech-
nique has excellent potential for on-line, real-time
analysis of recycled materials such as polyethylene tere-
phthalate, polyolefin, poly(vinyl chloride) and polystyrene.
Acknowledgements
This work was supported by Spanish Environmental
Government, projects: #241/2005/2B-2.7, #634/2006/2-
2.7 and #344/2007/3-2.7.
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