Construction and Building Materials 144 (2017) 525–531

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Effect of glycerol introduced into PLA based composites on the UV

weathering behavior
Shanshan Lv, Xiaojing Liu, Jiyou Gu ⇑, Yang Jiang, Haiyan Tan, Yanhua Zhang ⇑
Key Laboratory of Bio-based Material Science and Technology (Ministry of Education), College of Material Science and Engineering, Northeast Forestry University,
Harbin 150040, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 The crystal structure of starch/wood

flour/PLA composite was damaged
after UV weathering.
 Carboxylic acid was formed on the
surface of composite when
underwent UV weathering.
 Glycerol had a stabilize effect on the
UV durability of the composite.

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

Article history: Effect of accelerated weathering time and glycerol on the photodegradation behavior of starch/wood
Received 1 October 2016 flour/PLA composites was studied. The decreased intensity of diffraction peaks characterized by XRD indi-
Received in revised form 18 February 2017 cated that the crystal structure was damaged. The chemical structure changes characterized by FTIR
Accepted 27 March 2017
showed the formation of carboxylic acid. The decreased extent of the C@O absorbance intensity of the
Available online 5 April 2017
composite with 15% glycerol proved that glycerol had a stabilize effect on the UV durability of the com-
posites. After weathering, the maximum decomposition temperature decreased prominently due to the
Keywords:
chain cleavage. With the prolonged weathering time, the tensile and flexural strengths decreased
Poly (lactic acid)
UV weathering
gradually.
Degradation behavior Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction the biodegradable polymers, Poly (lactic acid) (PLA) is one of the
most promising plastics to replace the non-biodegradable plastics
The massive increase in the accumulation of non-biodegradable due to its biodegradable and renewable properties [2].
synthetic plastics has caused serious environmental pollution [1]. PLA is an aliphatic biodegradable polyester, which is derived
Therefore, most researchers have focused their attention on the from renewable resources such as cornstarch [3], and it can be
study of renewable and biodegradable polymer plastic. Among completely degraded by microorganisms under suitable conditions
[4]. However, the cost of PLA is still too expensive to be used
widely in daily life [5]. To overcome this drawback, blending PLA
⇑ Corresponding authors. with other polymers or fillers is an effective approach. Another
E-mail addresses: dldgujy@163.com (J. Gu), zhangyanhua@nefu.edu.cn drawback of PLA is its slow degradation rate. In order to accelerate
(Y. Zhang).

http://dx.doi.org/10.1016/j.conbuildmat.2017.03.209
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
526 S. Lv et al. / Construction and Building Materials 144 (2017) 525–531
the degradation of PLA, some natural polymers, such as starch and
wood flour, can be blended with PLA, due to their complete and
fast degradation rate in natural environment.
Polymer degradation is important not only in terms of the dura-
bility within its usability period, but also in terms of the post-
consumption period when it dominates the possibility of recycling
or utilization of the material [6]. As we all know, the polymers may
degrade when exposed to UV-light with the presence of air, which
will affect its service life [7]. Indeed, the material will suffer pho-
todegradation during its service life for outdoor applications [8].
UV irradiation may induce obvious physical-chemical changes in
polymers involving a reduction of molecular weight and a decrease
in mechanical performance [9].
PLA is a potential candidate to be used widely in future life.
Hence, the research of its weathering performance is important.
PLA is sensitivity to UV irradiation, moisture and temperature
(the influence factors of natural weathering) [10]. In recent years,
some studies have been performed on the UV weathering perfor-
mance of PLA [3,6,11,12] and PLA based composites [5,10,13–16].
Two photodegradation mechanisms have been reported. One of
the mechanisms is Norrish II-type cleavage which can lead to a
breakage of the backbone CAO bond [17–19]. As a result, the
new groups of C@C and carboxylic acid are formed, resulting in a
decrease in molecular weight [18]. The other mechanism indicates
that the reaction is random scission of main chains, its degradation
products are carboxylic acid and diketone groups [20].
As far, the research on UV ageing degradation of PLA and its
composites is widely, and the influence factors of the UV ageing
are various. The aim of this study is to analyze the influence of
glycerol on the weathering behavior of starch/wood flour/PLA com-
posites by comparing their mechanical properties, thermal behav-
ior, crystal properties and surface performance. Based on the
degradation behavior, the degradation regular can be evaluated,
which may provide a theoretic guide for the estimation of the ser-
vice life of PLA based materials.
2. Experimental
2.1. Materials
The PLA (306DX), purchased from Ningbo Huanqiu Plastic
Products Co., Ltd. (Ningbo, Zhejiang, China), is a semi-crystalline
extrusion material. The weight average molecular weight of
PLA was about 1.0  105–1.2  105, the melting index was
16–19 g 10 min 1, and the density of PLA was 1.2 ± 0.05 g cm 3.
Corn starch, industrial grade, was obtained from Dacheng Corn
Development Co., Ltd. (Changchun, Jilin, China). Wood flour (WF)
with particle sizes between 80 and 100 meshes was supplied by
Linyi Fengming wood flour factory (Shandong, China).
2.2. Processing procedure
All of the raw materials were dried at 50 °C for 8 h prior to use
in the vacuum oven in order to eliminate the moisture. The wood
flour and starch with the ratio of 3/7 (w/w) were well mixed for
15 min using a high-speed mixer. Then, 15% glycerol and PLA were
added to the mixture and the combination was evenly blended.
The final mixture was fed into a co-rotating twin-screw (L/D ratio
of 40, Nanjing Giant SHJ-20) set at 100 rpm to obtain the granules.
The temperatures at each zone were set at 135–150-170–170-
135 °C (from the feeder zone to the die). Afterwards, the standard
specimens according to ASTM D638-10 were processed by means
of injection molding (JPH180C, Guangdong ONLY Machinery Co.,
Ltd.). The temperature profile of injection molding was the follow-
ing: 180–180-170–170 °C. The injection pressure was kept at
65 MPa and mold temperature was kept at 30 °C. In this paper,
the composites with and without 15% glycerol were defined as
G0 and G15.
2.3. Accelerated weathering
In order to investigate the weathering behavior of starch/wood
flour/PLA composites, a UV ageing chamber (2 N-P, Maijie, Shang-
hai) was used. The weathering conditions were in accordance with
cycle 1 of the ASTM G154-06. Fluorescent lamps (UVA-340) with
0.89 W/m2/nm irradiance (at 340 nm) were used with cycles of
8 h UV exposure irradiation followed by a condensation period of
4 h. The accelerated weathering was performed for three periods:
300 h, 600 h, and 1200 h. After each period, the samples were
taken out from the chamber to analyze the performance.
2.4. Performance analysis of residual samples
2.4.1. X-ray diffraction (XRD)
The X-ray diffraction data were analyzed by using a X-ray
diffraction equipment (Rigaku D/max220, Japan). The genera-
tor was set up at 32 kV and 30 mA, using Cu-Ka radiation
(k = 0.1542 nm) as the X-ray source, together with a Ni-filter to
extract the Ka radiation. Diffraction patterns were collected over
a range of scattering angles (2h) of 5°–40°. All the measurements
were carried out at room temperature under atmospheric pressure.
2.4.2. Fourier transform infrared (FTIR)
A surface analysis by attenuated total reflectance (ATR) infrared
spectroscopy was carried out using a Bruker Tensor II instrument.
Scans were run at a resolution of 4 cm 1. For each sample, 32 scans
were recorded in the range of 400 cm 1–4000 cm 1.
2.4.3. Differential scanning calorimetry (DSC)
Thermal analysis was performed using a TA instruments Q20
under nitrogen atmosphere. The samples (5–6 mg) were heated
from room temperature to 200 °C at 10 °C/min with 50 mL/min
nitrogen flow.
2.4.4. Thermo gravimetric analysis (TGA)
The thermal stability of weathered starch/wood flour/PLA
composites was studied using a TG 209 F1 (NETZSCH, Germany).
Samples of approximately 5–10 mg were heated from room tem-
perature to 600 °C with 10 °C/min of heating rate and 50 mL/min
of nitrogen gas flow.
2.4.5. Mechanical properties
The mechanical strengths of composites before and after weath-
ering were performed at room temperature using a CMT-5504
Universal Testing Machine (Shenzhen SANS Test Machine Co.,
Ltd. China). The tensile strength was tested according to the ASTM
D638-10 method at a crosshead speed of 10 mm/min. The flexural
strength was measured according to the ASTM D790-10 at a cross-
head speed of 5 mm/min. A minimum of five specimens were
tested to obtain an average value.
3. Results and discussion
3.1. X-ray diffraction analysis
Fig. 1 shows the XRD patterns of the composites before and
after accelerated weathering. Before weathering, both the compos-
ites showed a diffraction peak at 2h = 16.7° which corresponded
to (1 1 0)/(2 0 0) plane of a phase for PLA [21]. Unlike other
literature, after weathering, the intensity at 16.7° decreased while
 S. Lv et al. / Construction and Building Materials 144 (2017) 525–531 527

Fig. 1. XRD diffraction patterns of composites at different weathering time, (a) G0; (b) G15.

it increased tremendously in other reports [10,22,23]. The G15
showed a slight increase in the peak intensity of 16.7°, while the
change of G0 was undetected. The reason for this may be that
the mobility of shorter chains obtained from chain scission was
stronger enough to crystallize with the presence of glycerol. With
further weathering, the peak intensity decreased gradually, indi-
cating that accelerated weathering destroyed the crystal structure
of PLA.
3.2. Surface chemical structure analysis
The chemical structure changes that occurred during the accel-
erated weathering were evaluated by FTIR. FTIR spectra of the
composites submitted to weathering over 0 h, 300 h, 600 h and
1200 h exhibited notable changes (Fig. 2) in some functional
groups after irradiation. In the spectrum of starch/wood flour/PLA
composite, the absorbance can be divided into five regions. The
absorption band at 1748 cm 1 corresponds to the stretching vibra-
tion of carbonyl groups C@O [24]. The absorption peak at
1451 cm 1 corresponds to deformation vibration of ACH3. The
peaks at 1382 cm 1 and 1360 cm 1 correspond to the symmetric
and asymmetric deformation vibration of CAH [25]. The peaks at
1182 cm 1, 1128 cm 1, 1080 cm 1 and 1042 cm 1 correspond to
stretching vibration of C-O [24]. The 865 cm 1 peak corresponds
to the stretching vibration of CACOO [6].
As shown in Fig. 2, none of the wavenumbers of the character-
istic bands shifted to higher or lower wavenumbers. After weather-
ing, only the intensity of the absorption bands changed. The
intensity of the C@O (1748 cm 1) and CAO stretching (1182–
1040 cm 1) bands gradually increased upon weathering especially
for 1200 h, showing strong evidence of photodegradation. As
reported, UV irradiation deteriorated the structure of PLA via ‘‘Nor-
rish type II photodegradation” [19,24], which formed carboxylic
acid and a new group of C@C. Hence, after UV weathering, the
intensity of C@O of both composites increased compared with that
of non-weathered composites. However, the band of C@C absor-
bance was only observed extremely tiny over 600 h weathering
in G0 (indicated by dash circle in Fig. 2(a)), but not as clear peak.
The change of CAO could also be induced by the degradation of
starch and wood flour in the composites, which resulted in an
increase in the intensity of CAO band. Another important factor
during accelerated weathering process was the humidity from con-
densation. It is known that hydrolysis also contributes to chain
scission especially in the CAO bonds of the ester structure in PLA
[26], which lead to a decrease in molecular weight and mechanical
properties.

Fig. 2. FTIR spectra of (a) G0; (b) G15 before and after different weathering times
528 S. Lv et al. / Construction and Building Materials 144 (2017) 525–531
The FTIR spectra of G0 and G15 showed similar changes after
weathering degradation, which indicated that same photodegrada-
tion products were formed for both composites and the glycerol
had no influence on the weathering mechanism of starch/wood
flour/PLA composites. Another concerned question was the effect
of glycerol on the photodegradation rate of starch/wood flour/
PLA composites. Fig. 3 shows the intensity variations of the car-
bonyl group after different weathering times. The increased extent
of the intensity of C@O is higher for G0 after 600 h weathering. This
means that the degradation rate of starch/wood flour/PLA compos-
ites decrease with the addition of glycerol, which suggests that
glycerol exhibit a stabilizing effect under UV weathering condition.
3.3. Thermal properties before and after accelerated weathering
DSC analysis was used to investigate the evolution of thermal
behavior of the composites at different weathering times, and the
transition temperatures obtained from first DSC heating scan were
presented in Table 1. From Fig. 4, the heating curves showed a
small endothermic peak around the glass transition temperature
(Tg) due to physical ageing or relax enthalpy [5]. It can be obviously
seen that the Tg and cold crystallization temperature (Tcc) of G15 is
lower than that of G0, which can be owed to the plasticization
effect of glycerol. With the increase of weathering time, the Tg tem-
peratures were found to increase from 60.7 °C and 57.2 °C to
65.1 °C and 64.1 °C for G0 and G15, respectively. The tendency of
the increasing Tg was observed in some other articles as well.
[27,28]. This phenomenon could be explained as follows: with
the further accelerated weathering, volume relaxation was induced
by the chains segmental motion, which resulted in a reduction of
the free volume. Therefore, more energy was required for the glass
transition, resulting in an increase in Tg [29].
The Tcc of G0 increased first and then decreased, while the Tcc of
G15 increased first and then remained unchanged. The first
increase in Tcc of G0 was probably induced by the crosslink of
the polymer chains and a strong interfacial bond formed between
the hydroxyl groups of starch, wood flour and the carboxyl groups
of PLA, decreasing the mobility, thus resulting in a stronger inhibi-
tory effect on the crystallization [30]. The following decrease in Tcc
of G0 was due to the enhanced molecular chain mobility caused by
chain scission (caused by UV irradiation) and hydrolysis (caused by
Fig. 3. FTIR spectra of (a) G0; (b) G15 before and after different weathering time in the region of 1700–1800 cm
condensation) during the further weathering process. Different
from G0, with the prolonged weathering, the Tcc of G15 kept a con-
stant value. It was because that the interfacial action between the
polymer chains was stronger with the presence of glycerol, which
could enhance the mobility of polymer chains to from cross-linked
site.
The shoulder in the endothermic melting peak was found to
merge for G0 composite while the shoulder was found to disappear
for G15 composite as the accelerated weathering time increased.
With the prolonged weathering, both the melting temperatures
of Tm1 and Tm2 for the composites showed an increase tendency
(Table 1). This tendency was different from some other reports that
had a decrease in its melting temperature [27,31]. The reason may
be that the initial crystal of PLA was imperfect and more defects
existed, after degradation, the segmental mobility increased, thus
more chains rearranged into the crystal lattice, resulting in an
increase in the melting temperature.
3.4. Thermal stability of composites before and after accelerated
weathering
TGA was used to assess the variations in thermal stability of G0
and G15 at each accelerated weathering period. The onset degrada-
tion temperature (Ton), maximum mass loss temperature (Tp) and
final degradation temperature (Tend) determined from TGA curves
(Fig. 5) were listed in Table 2. As illustrated in Fig. 5 and Table 2,
with the prolonged weathering, the Ton of both composites
decreased after 300 h weathering followed by an increase after
600 h weathering, finally decreased again after 1200 h weathering.
The first decrease of Ton for the composites was due to the degra-
dation of polymers induced by 300 h weathering. Then, the Ton
had a slight increase, owing to the degradation of amorphous
region and the resistance to degradation of the remained crystal
structure. Meanwhile, after 600 h weathering, more low molecular
chains were formed, which had better mobility to form cross-
linked bonds. All the mentioned reasons above would result in a
higher degradation temperature. After 1200 h weathering, most
molecular chains were degraded and the structure of the polymers
had already changed due to the chain scissions and hydrolysis,
which led to a decrease in thermal stability.
1
.
 S. Lv et al. / Construction and Building Materials 144 (2017) 525–531 529

Table 1
Transition temperatures obtained from first heating thermograms of DSC.

Time (h) Tg (°C) Tcc (°C) Tm1 (°C) Tm2 (°C)

G0 0 60.7 96.7 – 154.7
300 61.9 106.2 144.5 155.7
600 62.3 104.8 148.5 157.1
1200 65.1 102.9 148.5 157.1
G15 0 57.2 93.2 139.2 150.8
300 61.3 97.2 144.4 155.0
600 61.7 97.2 145.9 155.9
1200 64.1 97.3 146.2 156.6

Fig. 4. DSC first heating thermograms of composites at different weathering time, (a) G0; (b) G15.

Fig. 5. TGA curves of the composites at different weathering time, (a) G0; (b) G15.

Compared with the non-weathered composites of G0, the max-
imum mass loss temperature decreased prominently due to the
degradation caused by the photolysis and hydrolysis of polymer
chains. However, the Tp of G15 had no obvious change after
600 h weathering, while had a decrease about 5 °C after 1200 h
weathering compared with the non-weathered composites of
G15. The differences of Tp variation of G0 and G15 indicated that
the glycerol in the composites of G15 had an inhibition effect on
the weathering degradation of starch/wood flour/PLA composites.
The Tend of weathered G0 was lower than that of non-weathered
G0, while for G15 the drop was less significant. This phenomenon
was consistent with the changes of Tp for the composites, which
proved the statement that glycerol had an inhibition effect on
the weathering degradation.
3.5. Mechanical properties of the composites before and after
accelerated weathering
The variations in tensile strength and flexural strength of the
composites after different weathering time are presented in
Fig. 6. Both the tensile strength and flexural strength of the com-
posites showed a decrease trend after accelerated weathering
530 S. Lv et al. / Construction and Building Materials 144 (2017) 525–531
Table 2
Thermogravimetric data of the composites after different weathering times.
Time (h) Ton (°C)
G0 0 300.1
300 288.9
600 291.3
1200 285.3
G15 0 291.1
300 288.0
600 291.4
1200 279.7
Fig. 6. Mechanical strengths of the composites at different weathering time, (a) G0; (b) G15.
(Fig. 6). The reduction in tensile and flexural strength of the com-
posites with the prolonged weathering time was considered to
be due to plasticization [23], hydrolysis [10] and photochemical
degradation [10]. As for the tensile strength, the G0 had a slight
higher tensile strength than that of G15 after different weathering
periods, which was probably attributed to the existence of glycerol
that acted as a plasticizer. The composites of G0 and G15 exhibited
a similar flexural strength (64.0 MPa and 63.5 MPa) when the com-
posites were non-weathered. However, during the same weather-
ing period, the reduction in flexural strength of G0 was lower
than that of G15, such as the decrease of flexural strength for G0
was 27.3% while that for G15 was 40.8% after 1200 h weathering.
The reason of this can be owed to the migration of the glycerol dur-
ing the weathering period, which had a weaken effect on the flex-
ural strength. In addition, according to XRD, the crystallinity of G15
was lower than that of G0, which had less resistance effect on the
degradation, resulting in a faster degradation for G15.
4. Conclusions
The influences of weathering time and glycerol on the
weathering degradation behavior of starch/wood flour/PLA com-
posites were estimated comprehensively. The crystal structure
was destroyed by the photodegradation during UV irradiation pro-
cess, which exhibited a decrease intensity in the diffraction peaks.
The increase in absorbance intensity of C@O band indicated that
the carboxylic acid was one of the photodegradation products.
The Norrish type II mechanism was the most possible degradation
route. However, the C@C band could not be clearly detected by the
FTIR except the weathered G0. The presence of glycerol exhibited a
stabilize effect on the weathering of starch/wood flour/PLA com-
posite. However, the glycerol did not influence the photodegrada-
tion mechanism of the composite. The maximum thermal
decomposition temperature, tensile strength, and flexural strength
showed a decrease trend due to the chain cleavage caused by
Tp (°C) Tend (°C)
320.1 342.5
312.1 330.9
312.3 335.1
306.6 332.3
319.4 336.4
320.9 339.4
320.8 338.4
314.6 334.1
photodegradation. Based on these results, it can provide an effec-
tive method to adjust the weathering degradation rate, and sup-
port theoretical guidance for the recycling and application of PLA
based materials.
Acknowledgements
Thanks for the finical support of the Fundamental Research Funds
for the Central Universities (Nos. 2572016DB01; 2572016AB17).
This work was also thanks for the National Forestry Public Welfare
Industry Major Projects of Scientific Research (No. 201504502) and
the National Natural Science Foundation of China (No. 31670569).
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