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Polymer Testing
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Analysis Method
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.
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 Nowadays, the identification of plastic materials in the
analysis of recycled materials, which is really of interest recycling industry is an important need because of the in-
in order to obtain plastics separation faster and more effec- crease of plastic waste. Hence, the compounds chosen for
tively. A Nd:YAG laser has been used for other applications study were commercial plastics.
due to its simplicity, easy operation, high efficiency and low In this study, the emission lines chosen for C, H, O and N
cost. Despite all works and publications on LIPS that have are 247.9 nm, 656.3 nm, 777.2 nm (triplet) and 746.8 nm,
appeared in recent years, the laser plasma can offer new respectively, and the molecular bands for C2 and CN are
advantages for plastics identification and separation in ac- 516 and 388 nm, respectively.
cordance with new exigencies of polymer industry and
science. 2. Experimental
In previous papers about plastic [28] and geological ma-
terials [29], we have shown that simple statistical correla- 2.1. Instrumental setup
tion methods, such as linear and rank correlations, can be
successfully applied for identification of materials. A com- The instrumentation used consisted of a Nd:YAG laser,
pact LIP spectrometer was used for instant identification a xyz stage carrying the sample (Standa 011957), a spectro-
of materials. Spectra were collected with a compact dual graph and an intensified charge coupled device (ICCD) de-
channel fibre optic spectrometer and monitored either in tector. A diagram of this instrumentation is shown in Fig. 1.
a 230–310 nm spectral window for geological material or A Nd:YAG laser (Brilliant Quantel, Q-Switched) with
a 200–800 nm spectral window for plastic material. Both a 115 mJ laser pulse energy at the second harmonic of
studies were carried out applying parametric (linear) and 532 nm, a 4.4 ns pulse duration and 0.7 Hz repetition fre-
nonparametric (rank) correlation methods for identifica- quency was used with a 90 mm focal length lens. The crater
tion of compounds; and a nearly 100% reliable identifica- diameter was 0.4 mm. The plasma light was collected and
tion was achieved. transported to the spectrograph by lens and optical fibre
In this study, the objective is to identify plastic materials (fused silica, 50 mm core diameter). An external collector/
by determining the intensity ratios from elemental lines collimator was used as a collector lens, its position being
and molecular bands. Measurements are made of the ratios adjusted at 200 mm by a diode laser (Andor, HE-OPI-
of several elements and molecular species, such as C1, H, N, 0009). An Echelle spectrograph (Andor Mechelle ME5000,
O, C2 system (Swan bands) and CN. focal length 195 mm, F/7, l/Dl 5000, spectral range from
Molecular materials like plastics are almost entirely at- 200 to 975 nm) was coupled to an ICCD detector (Andor
omized when exposed to intense laser radiation. This im- iStar DH734, 1024 1024 pixels, 13.6 13.6 mm2/pixel,
plies that limitations exist in application of LIPS for 18 mm diameter intensifier and the exposure time was
identification of polymers because of the loss of molecular 0.011 s). This system was calibrated by a Hg:Ar lamp (Ocean
information in the plasma [29]. In the present work, peak Optics, HG-1, Hg–Ar lines 253–922 nm). The MCP gain was
ratio analysis in combination with analysis of molecular fixed at 180. A measurement gate delay time of 1 ms and an
bands was used for the identification of energetic materials. integration time of 1.5 ms were used.
The intensity ratio is related to the difference between the
upper energy levels of the lines and is also proportional to 2.2. Samples and sample preparation
the ratio of Boltzmann factors, becoming independent of
the ablated mass [41]. Therefore, it is expected to yield Little sample preparation was necessary. This results in
better results than the single peak intensity alone. increased throughput, greater convenience and fewer
opportunities for contamination to occur. The polymers deviation and RSD %, with all ratios checked by a simple
studied were: polyethylene terephthalate (PET), polyethyl- Grubbs test.
ene (PE), high-density polyethylene (HDPE), low-density
polyethylene (LDPE), polypropylene (PP), polystyrene (PS) 3. Results and discussion
and poly(vinyl chloride) (PVC).
Their formula, chemical structure and theoretical ratios 3.1. Choice of analytical bounds and lines
are shown in Table 1. A small piece of plastic (approxi-
mately 3 3 cm) was placed on double-sided tape stuck The C2 Swan system and the CN band, as well as the car-
to a glass slide. The piece of plastic must be completely bon, hydrogen, oxygen and nitrogen, emission intensity ra-
stuck to the slide in order to avoid air between them. Three tios were the necessary parameters to identify organic
determinations were carried out for each sample. Each de- compounds. Oxygen, nitrogen and hydrogen emission lines
termination is the average of ten shots and the discrep- and a number of molecular bands are used for this task. The
ancies were evaluated by a simple Grubbs test (p ¼ 0.05). analysis of molecular bands [42,43] is focused on the detec-
This test is shown in Eq. (1), where Xi is the value studied, tion of CN molecular violet bands at 386.17 nm, 387.14 nm
X is the average and s is the standard deviation. 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
O O
* 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
* CH CH2 *
n
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
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)
388 nm and C2 at 516 nm. These are the most intense lines Under our experimental conditions, atmospheric nitro-
covered by our spectrometer and; in addition, these lines gen and oxygen influence the spectra. Therefore, nitrogen
are free from spectral interference. The Echelle spectro- and oxygen signals appear in compounds without these el-
graph allowed us to obtain the signal ratios free of sample ements and, similarly, it occurs with the CN band. A better
matrix, laser and detector fluctuations, because it is able to approach would be to use an inert atmosphere, for exam-
use a wide spectral window (from 200 to 975 nm) with ple, helium or argon. However, our objective is to analyse
very high resolution (0.1 Å), detecting simultaneously all polymer in recycling industrial conditions where a helium
elements and bands without overlapping. 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)
Table 2
Summary of the results obtained in the characterisation of plastics using ratios
(RSD %).
710 J. Anzano et al. / Polymer Testing 27 (2008) 705–710