Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Instituto Politcnico Nacional, CICATA-Altamira, Km. 14.5 Carretera Tampico-Puerto Industrial Altamira, 89600 Altamira, Tamps, Mexico
PMTA of CICATA-Altamira, IPN, Km. 14.5 Carretera Tampico-Puerto Industrial Altamira, 89600 Altamira, Tamps, Mexico
c
Centro Nacional de Investigaciones Metalrgicas, CENIM (CSIC), Av. Gregorio del Amo 8, 28040 Madrid, Spain
b
a r t i c l e
i n f o
Article history:
Received 4 August 2014
Received in revised form 18 October 2014
Accepted 23 October 2014
Available online 6 November 2014
Keywords:
PET/PLA
PET/chitosan
Blends
Miscibility
Degradability
a b s t r a c t
This work reports the synthesis and miscibility of PET/PLA and PET/chitosan blends as well
as their degradation in real soil environment (6 months) and in accelerated weathering
(1200 h). For this purpose, commercial polyethylene terephthalate (PET) and recycled
PET (R-PET) were used as polymer matrixes and extruded with different amounts of polylactic acid (5, 10 and 15 wt-%) or chitosan (1, 2.5 and 5 wt-%) to form laments. Different
characterization techniques such as X-ray diffraction (XRD), Fourier transform infrared
spectroscopy (FTIR), differential scanning calorimetry/thermogravimetric analysis (DSC/
TGA) and scanning electron microscopy (SEM) were used before and after degradation process. The results indicate weak interactions between blend components suggesting secondary bonds by hydrogen bridges or by electrostatic forces. The miscibility of chitosan in both
PET matrixes is lower in comparison with PLA; the saturation of PLA into polymer matrixes
was reached up to an amount of 10 wt-% whereas longer amounts of 5 wt-% of chitosan
become rigid and brittle. The best performance in the miscibility and degradation process
was found for PET/chitosan (95/5) which is comparable with commercial bottles of BioPET
under similar experimental conditions.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
The long-lasting petroleum polymers have been widely
used provoking that the waste of this kind of polymers
takes a very long time to be broken down. Nowadays, this
indiscriminate use of petroleum-based polymers has
caused a big pollution problem [1,2]. To reduce this
problem, it has been used biodegradable polymers from
renewable sources like collagen, keratin, gluten, milk proteins, soy proteins, polysaccharides like starch, cellulose
derivatives, chitosan, alginate, carrageenan, pectins. These
Corresponding author. Tel.: +52 8332600125x87510; fax: +52
8332600125x87521.
E-mail
addresses:
atorresh@ipn.mx,
atohuer@hotmail.com
(A.M. Torres-Huerta).
http://dx.doi.org/10.1016/j.eurpolymj.2014.10.016
0014-3057/ 2014 Elsevier Ltd. All rights reserved.
286
2. Experimental
2.1. Materials and processing
During the rst set of experiments, it was used a commercial PET (CLEARTUF-MAX2, lot no. 1008-03219) provided as pellets by M&G Polymers Company whereas in
the second step recycled PET (R-PET) was obtained from
discarded bottles after they were washed, dried and cut
into akes. The polylactic acid pellets, PLA-2002D (containing 4.4 wt-% in average of isomer D), (batch: YA0828b131)
and chitosan (low molecular weight, with a deacetylation
degree P75%) were purchased from NatureWorks LLC,
USA and Sigma Aldrich, respectively. Before processing,
the raw materials were dried at 60 C during 24 h in an
oven (Thermolyne). Different amounts of PLA (5, 10 and
15 wt-%) or chitosan (1, 2.5 and 5 wt-%) and commercial
PET or R-PET were hand mixed previous to extrusion process. It is important to mention that, initially, we tried to
add into the polymer matrix the same quantities of chitosan or PLA (5, 10 and 15 wt-%), unfortunately, we observed
that synthesized samples with chitosan become rigid and
brittle, regarding the chitosan polymer is a brittleness
material, however, this characteristic depend if the material is derived of fungal biomass, crustacean shell and
insect cuticles [20,21]. Thus, after several experiments we
found that an optimal percentage to evaluate chitosan is
less than 5 wt-%. Blends with a laments shape (1 mm in
diam. 200 cm length) were obtained in a single-screw
extruder (C.W. Brabender) with L/D ratio of 25:1 and four
heating zones: feeding (225 C), compression (237.5 C),
distribution (260 C), and nally, the extrusion die
(225 C).
2.2. Characterization
Structural characterization of the polymer blends was
carried out using a Bruker D8 Advance diffractometer from
2h = 560 (Cu Ka, k = 0.154 nm) and a rate of 1.5 /min.
The Fourier Transform Infrared Spectroscopy (FT-IR)
spectra were recorded with a Nicolet FT-IR spectrometer
(Magna System 550) equipped with an attenuated total
reectance (ATR) accessory between 2000 and 650 cm1
at an optical resolution of 4 cm1 (40 scans).
Simultaneous thermal analysis was carried out in a
Labsys Evo, Setaram instrument, which was used in the
DSC/TGA conguration with the sample and reference crucibles made of a-Al2O3. Sample amount in the crucible was
about 10 mg. The samples were rstly heated at 40 C and
hold for 2 min and subsequently, the measurements were
carried out in the range of 40300 C to evaluate thermal
degradation under argon atmosphere with a heating rate
of 10 C/min. Then, the samples were hold at 300 C for
2 min followed by a cooling with the same rate. It is well
known that peak temperature is inuenced by the scan
rate; however, in this case such displacement was considered neglected. It is also important to mention that DSC
heating was intentionally evaluated from 40 C to 300 C
in order to observe the total degradation of these samples.
After accelerating weathering tests, DSC/TGA analysis were
also conducted on the samples with similar procedure and
heating rate but using a temperature range from 40 C to
500 C.
In order to dissolve the biopolymer phase and to evaluate the dispersion in the different matrixes (PET and R-PET)
as well as evaluate the morphology of the as-prepared
samples, the polymer blends were solubilized in chloroform and acetic acid for PLA and chitosan, respectively.
The dissolved samples were observed by SEM to analyze
the cross section of the blends; before characterization,
287
(100)
(110)
(002)
(100)
(210)
(102)
(300)
(112)
(111)
(201)
(203)
(110)
PLA
20
30
40
50
60
(100)
(110)
(111)
(011)
(b)
(010)
2 (degrees)
PET/PLA 95/5
PET/PLA 90/10
PET/PLA 85/15
R-PET/PLA 95/5
R-PET/PLA 90/10
R-PET/PLA 85/15
10
20
30
40
50
60
(100)
(110)
(111)
(c)
(010)
2 (degrees)
Intensity (a.u.)
{(200)
10
Chitosan
(011)
R-PET
Intensity (a.u.)
PET
Intensity (a.u.)
(a)
(111)
(011)
(010)
PET/Chitosan 99/1
PET/Chitosan 97.5/2.5
PET/Chitosan 95/5
R-PET/Chitosan 99/1
R-PET/Chitosan 97.5/2.5
R-PET/Chitosan 95/5
10
20
30
40
50
60
2 (degrees)
Fig. 1. X-ray diffraction patterns for (a) Raw materials (b) PET/and R-PET/
PLA (c) PET/and R-PET/chitosan.
288
289
(b)
(a)
C-C CO 1,4 CH
C=O
C-H
Absorbance (%)
PET
C-C C-C CH CO1,4
2
CH
C=O
CH
C-H
R-PET
C=O
C-H CO
C-O
C-C
C-H
PET/PLA 95/5
Absorbance (%)
= Phenyl group
PET/PLA 90/10
PET/PLA 85/15
R-PET/PLA 95/5
PLA
chitosan
Amide I and II
N-H
CH2
C-N
C-O
C=O PLA
3500
3000
2500
2000
1500
C=O PET
PET signals
R-PET/PLA 85/15
COC
4000
R-PET/PLA 90/10
3000
1000
2500
2000
1500
1000
-1)
-1)
Wavenumber (cm
Wavenumber (cm
(c)
Absorbance (%)
PET/chitosan 99/1
PET/chitosan 97.5/2.5
PET/chitosan 95/5
R-PET/chitosan 99/1
R-PET/chitosan 97.5/2.5
R-PET/chitosan 95/5
3000
2500
2000
1500
1000
Wavenumber ( cm -1)
Fig. 2. ATR- FTIR for (a) Raw materials (b) PET/and R-PET/PLA (c) PET/and R-PET/chitosan.
Table 1
Thermal transitions obtained for as-prepared selected blends using PLA and
chitosan with PET and R-PET.
Sample
Tg (C)
Tm (C)
Tc (C)
PET
R-PET
PLA
Chitosan
PET/PLA 95/5
PET/PLA 90/10
PET/PLA 85/15
R-PET/PLA 95/5
R-PET/PLA 90/10
R-PET/PLA 85/15
PET/chitosan 99/1
PET/chitosan 97.5/2.5
PET/chitosan 95/5
R-PET/chitosan 99/1
R-PET/chitosan 97.5/2.5
R-PET/chitosan 95/5
82
69
88
126, 243
245
161
188
250
250
250,158
250
250
250,158
248
249
251
248
250
250
201
205
126
200
202
205
198
201
202
197
197
203
208
207
208
290
Weight loss%
Wi Wr
Wi
Degradation rate
KW
ATD
291
(a)
PET
10 m
(b)
(d)
(c)
PET/PLA 95/5
5 m
(e)
PET/PLA 90/10
5 m
(f)
R-PET/PLA 95/5
5 m
(h)
5 m
R-PET/PLA 90/10
(k)
PET/chitosan
97.5/2.5
5 m
R-PET/chitosan
97.5/2.5
R-PET/PLA 85/15
5 m
(j)
5 m
PET/chitosan 95/5
5 m
(m)
(l)
R-PET/chitosan 99/1 5 m
5 m
(g)
(i)
PET/chitosan 99/1
PET/PLA 85/15
5 m
R-PET/chitosan 95/5 5 m
Fig. 3. Morphological features of selected blends using PLA and chitosan with PET and R-PET.
accelerated weathering equaling to a year of natural weathering is used as a conservative data in this work [57].
Table 2 indicates the lifetime prediction of the synthesized materials studied in this work. The results estimate
that commercial PET will totally decompose in about
125 years whereas R-PET and B-PET decomposes in 76
and 86 years, respectively. As previously mentioned, this
is consistent with the strong dependency of being
semicrystalline B-PET and amorphous R-PET. From overall
samples, R-PET blends with chitosan (95/5) and PLA (85/
15) were found to degrade faster than the others compositions after 45 and 54 years, respectively.
292
3,0
B-PET
R-PET
PET
PET/PLA
R-PET/PLA
PET/chitosan
R-PET/chitosan
PLA
2,5
2,0
1,5
95/5
97.5/2.5
85/15
85/15
99/1
90/10
95/5
B-PET
R-PET
95/5
97.5/2.5
90/10
95/5
PET
1,0
99/1
0,5
PLA
0,0
0
200
400
600
800
1000
1200
1400
Time (h)
Fig. 4. Weight loss% of PET, R-PET, B-PET, PLA and blends under
accelerated weathering.
R-PET/chitosan 95/5
R-PET/chitosan 97.5/2.5
R-PET/chitosan 99/1
PET/chitosan 95/5
Blends
PET/chitosan 97.5/2.5
PET/chitosan 99/1
R-PET/PLA 85/15
R-PET/PLA90/10
R-PET/PLA 95/5
PET/PLA 85/15
PET/PLA90/10
PET/PLA 95/5
0,0
1,0x10
-3
2,0x10
-3
3,0x10
-3
4,0x10
-3
Table 2
Lifetime prediction of raw materials and blends.
Sample
PET
R-PET
B-PET
PET/PLA 95/5
PET/PLA 90/10
PET/PLA 85/15
R-PET/PLA 95/5
R-PET/PLA 90/10
R-PET/PLA 85/15
PET/Chitosan 99/1
PET/Chitosan 97.5/2.5
PET/Chitosan 95/5
R-PET/Chitosan 99/1
R-PET/Chitosan 97.5/2.5
R-PET/Chitosan 95/5
125
86
76
107
103
76
91
58
54
143
93
60
56
55
45
293
(a)
(b)
Absorbance (%)
Absorbance (%)
PET-PLA 95/5
PET-PLA 90/10
C=O(c)
1747
C-O
C=O(a)
1700
PET-PLA 85/15
2000
1800
R-PET/PLA 95/5
R-PET/PLA 90/10
R-PET/PLA 85/15
1600
1400
1200
1000
800
2000
1800
1600
(c)
1000
800
(d)
PET/chistosan 99/1
Absorbance (%)
Absorbance (%)
1200
Wavenumber (cm )
Wavenumber (cm )
PET/chistosan 97.5/2.5
C=O (c)
1746
1800
R-PET/Chitosan 99/1
R-PET/Chitosan 97.5/2.5
1715
C=O (a)
1700
CH2
PET/chistosan 95/5
2000
1400
-1
-1
1600
1400
C-O
1200
1000
R-PET/Chitosan 95/5
800
2000
1800
1600
1400
1200
1000
800
Wavenumber (cm-1 )
-1
Wavenumber (cm )
Fig. 6. FTIR spectra of: (a) PET/PLA, (b) R-PET/PLA, (c) PET/chitosan and (d) R-PET/chitosan blends after being exposed to accelerated weathering for 1200 h.
Table 3
Thermal properties of raw materials and blends after being subjected to accelerated weathering.
Sample
Tm(PLA) (C)
Tg(chitosan) (C)
Tc (C)
Tm(PET) (C)
Td(chitosan) (C)
Td(PLA) (C)
Td(PET) (C)
PET
R-PET
PLA
Chitosan
PET/PLA 95/5
PET/PLA 90/10
PET/PLA 85/15
R-PET/PLA 95/5
R-PET/PLA 90/10
R-PET/PLA 85/15
PET/Chitosan 99/1
PET/Chitosan 97.5/2.5
PET/Chitosan 95/5
R-PET/Chitosan 99/1
R-PET/Chitosan 97.5/2.5
R-PET/Chitosan 95/5
170
156
120
248
227,245
150
152
152
155
152
152
152
115,
117, 165
117, 171
205
202
200
194
180
180
184
191
190
243
242
244
241
243
239
240
242
249
241
240
340
343
344
340
370
370
370
370
370
370
424,436
424
421
422
422
422
420
421
422
422
Since chitosan was used as powder, DSC data after accelerated weathering was not included.
peak appear at about 227 C and a Tm that remains constant. The crystallization temperature of the PET and
R-PET was found lower than before the weather chamber
tests. The observed shifts in the Tcs were directly corre-
294
melting point corresponding to PLA as well as the endothermic peak at 370 C corroborates that the degradation
of PLA is taking place even with low PLA concentrations
[70].
In Chitosan, there are several glass transition temperature values, this variability could be attributed to different
factors like physical state, molecular weight and de-acetylation degree [71]. From the Table 3, when chitosan was
added to polymer matrixes two glass transition temperatures appear, one at 115 and 117 C from the plasticized
chitosan as a result of the water supplied in the weathering
test, and the second one at 165 and 171 C attributed to
increase of the molecular movement due to dissociation
of hydrogen bonds and starting of molecular scissions
[72]. The DSC studies of the blends with chitosan also
showed a degradation temperature at 340 C. This
endothermic peak can be attributed to the degradation of
chitosan [68,73] and its effect into the PET matrix. Thus,
both PLA and chitosan biopolymers induce the scission of
PET bonds, producing shorter fragments and therefore,
provoking the PET degradation at 420 C [74].
Thermal stability of the polymer blends after
accelerated weathering and weight loss as a function of
temperature was analyzed by TGA (Fig. 6ad).
(a)
80
PET
PET/PLA (95/5)
PET/PLA (90/10)
PET/PLA (85/15)
60
100
100
PLA
40
20
(b)
80 R-PET/PLA (95/5)
R-PET/PLA (90/10)
60 R-PET/PLA (85/15)
PLA
40
20
0
100
200
300
400
500
Temperature (C)
Temperature (C)
(c)
100
100
R-PET
80
60
40
20
0
100
PET/Chitosan (95/5)
PET/Chitosan (97.5/2.5)
PET/Chitosan (99/1)
PET
200
300
400
Temperature (C)
(d)
80
60
40
20
500
0
100
R-PET/Chitosan (95/5)
R-PET/Chitosan (97.5/2.5)
R-PET/Chitosan (99/1)
R-PET
200
300
400
500
Temperature (C)
Fig. 7. TGA thermograms of: (a) PET/PLA, (b) R-PET/PLA, (c) PET/chitosan and (d) R-PET/chitosan blends after being exposed to accelerated weathering for
1200 h.
295
100 m
(a)
PET/PLA 95/5
(b)
10 m
(d)
R-PET/PLA 95/5
(c)
PET/PLA 90/10
10 m
(g)
PET/chitosan 99/1 10 m
(j)
R-PET/chitosan 99/1 10 m
R-PET/PLA 90/10
10 m
10 m
10 m
PET/chitosan 95/5 10 m
(l)
(k)
R-PET/chitosan
97.5/2.5
R-PET/PLA 85/15
(i)
(h)
PET/chitosan
97.5/2.5
10 m
(f)
(e)
10 m
PET/PLA 85/15
10 m
R-PET/chitosan
95/5
10 m
Fig. 8. PET/PLA, R-PET/PLA, PET/chitosan and R-PET/chitosan blends with different weight ratios after 900 h of accelerated weathering.
0.004
R-PET/Chitosan (95/5)
R-PET/Chitosan (97.5/2.5)
R-PET/Chitosan (99/1)
PET/Chitosan (95/5)
R-PET/PLA (85/15)
R-PET/PLA (95/5)
R-PET/PLA (90/10)
PET/Chitosan (99/1)
0.000
PET/PLA (85/15)
0.001
PET/PLA (90/10)
0.002
PET/Chitosan (97.5/2.5)
0.003
PET/PLA (95/5)
Fig. 8al shows micrographs of representative weathered blends after 1200 h. The micrographs of the weathered laments evidenced rough surfaces caused by the
effects of the UV light and water that simultaneously cause
surface microcracks; initially, microcracks or ssures were
formed due to the breaking of the backbone CAO bonds
and thereafter are dispersed in different points of the surface. The morphology was quit affected by the PLA amount,
producing further degradation. For damage accumulation,
some regions are so weakened that cracking formation
starts microcracks and expanding over all surface of laments (inset of Fig. 8c). Thus, in presence of PLA and after
this biodegradable polymer begins to degrade, PET starts
the disintegration process in ACAOA and AC@O bonds
[77], which are produced from cleavage at CAC bonds of
the main polymer chain [78]. In Fig. 9, it is shown a proposed model for photo-oxidative degradation of polymer
blends where are illustrated the chemical alterations and
crack formation during weathering test.
By comparison of the morphologies of PLA and chitosan,
it is shown that chitosan blends presented small quantity
of microcracks (Fig. 8gl); however, some deep holes
formed by the swelling of chitosan powders were also evident. The swelling may be caused by the water used in the
QUV camera, leaving away the chitosan particles which
produce the microcracks [79]. In this case, the photo-oxidation process of PET/chitosan blends occurs due to alterations such as cross-linking and chains scission; i.e. the
formation of carboxylic groups increasing the amount of
polar groups on the surface during and after irradiation
time point out both the photo-oxidation of chitosan and
changes of its structure. Additional groups such as OH,
OOH, CO can also contribute to the rapid degradation of
chitosan with the subsequent swelling and cracks formation and in consequence, eventually, the PET disintegration
[80].
296
297
(a)
80
100
PET
PET/PLA (95/5)
PET/PLA (90/10)
PET/PLA (85/15)
60
PLA
40
20
0
100
200
(b)
300
400
R-PET/PLA (95/5)
60 R-PET/PLA (90/10)
40 R-PET/PLA (85/15)
PLA
20
0
100
500
200
Temperature (C)
(c)
100
80
60
PET
40
PET/Chitosan (99/1)
20
200
300
400
400
500
500
Temperature (C)
(d)
80
60
40
R-PET
R-PET/Chitosan (99/1)
20
PET/Chitosan (97.5/2.5)
PET/Chitosan (95/5)
0
100
300
Temperature (C)
100
R-PET
80
100
R-PET/Chitosan (97.5/2.5)
R-PET/Chitosan (95/5)
0
100 150 200 250 300 350 400 450 500
Temperature (C)
Fig. 11. Thermograms for (a) PET/PLA, (b) R-PET /PLA, (c) PET/chitosan and (d) R-PET/chitosan in composting for 6 months.
384 C whereas with other ratios the decomposition temperature remains fairly constant, corroborating the loss
weight in soil.
According to the above results, the addition of higher
amounts of PLA or chitosan on both PET matrixes can
modied its degradation mechanism. PLA degradation at
temperature between 3040 C and 80-% of humidity
could be due to the chemical hydrolysis that provokes that
eventually the PET/PLA blends cleavage and degrades; similarly chitosan is degraded by the oxygen presence due to
the interaction in the water drop/surface of the blend samples interface.
4. Conclusions
Blends of commercial and recycled PET/PLA and -/
Chitosan were prepared by extrusion process at 250 C to
analyze the miscibility and degradability as a function of
biopolymer content. The following conclusions can be
drawn:
After extrusion process, XRD patterns and infrared spectra analysis showed a weak interaction between PET
matrixes and biodegradable polymers suggesting type secondary bonds by hydrogen bridges or by electrostatic
forces. In independence of the amount of biodegradable
polymers, their semi-crystalline character helps to the
recrystallization of R-PET during the extrusion reprocess-
298
299