RSC Advances

View Article Online

PAPER View Journal | View Issue

From waste to functional additives: thermal

stabilization and toughening of PVA with lignin
Published on 26 January 2016. Downloaded by Sichuan University on 9/17/2020 8:05:12 AM.

Cite this: RSC Adv., 2016, 6, 13797

Xiao-Qin Hu,ab De-Zhan Ye,c Jin-Bo Tang,ab Lin-Jie Zhangab and Xi Zhang*ab

Received 10th December 2015
Accepted 20th January 2016
DOI: 10.1039/c5ra26385a
www.rsc.org/advances
Blend films of poly(vinyl alcohol) (PVA) and a graft copolymer (GL) of acrylic acid (AA) with eucalypt lignosulfonate
calcium (HLS) were prepared by using a solution casting method. The structure of GL/PVA blend films was
confirmed by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy and scanning electron
microscopy (SEM), which indicate that GL/PVA is a homogeneous system due to the strong interactions
between PVA and GL. Differential scanning calorimetry (DSC) results indicate that only one glass transition
temperature (Tg) can be seen over the entire blending ratio. Meanwhile, the Tg was enhanced and the melting
point (Tm) was depressed when GL was added to PVA. With the addition of 3 wt% GL, the onset
decomposition temperature (To) was increased by 102
C compared to that of PVA. Compared with pure
PVA, the GL/PVA exhibited a remarkable improvement in mechanical properties: the tensile strength and
Young’s modulus of GL/PVA with 5 wt% GL were 39% and 285% higher than that of pure PVA, respectively.
These results show that a new melt-processing method of PVA may be developed by the addition of GL in PVA.

Usually, the maximum (Tmax) or onset decomposition (Tonset)

1 Introduction
Poly(vinyl alcohol) (PVA) is widely used in many applications such
as medical treatments, construction materials, and household
industries because of its low cost and many excellent properties
including mechanical performance, solvent resistance, biocom-
patibility and biodegradability.1 Until now, two technologies,
thermal processing and solution processing, have been adopted
for PVA. Despite its excellent water solubility, the casting proce-
dure of PVA is still time-consuming and uneconomical. Thus,
there is particular interest in obtaining PVA products through
melt extrusion or injection. Because of the strong inter- or
intramolecular hydrogen bonding in PVA, its thermal processing
window is very narrow, resulting in simultaneous decomposition
during the extrusion process.2 Lowering PVA melting point by the
incorporation of plasticizers could resolve this problem to some
extent.3,4 Nevertheless, this approach is unsatisfactory for entirely
overcoming the problem of the thermal decomposition of PVA
without sacricing it’s physical properties. In contrast to plasti-
cization, the improvement of PVA thermal stability with llers
might offer a promising way for achieving its melt extrusion. For
example, magnesium chloride, calcium oxide and silica show
a thermal retardation effect on PVA.2,5,6 Similar results were also
observed with the addition of nano-llers.7–11 However, their
effects on improving PVA thermal stability are rather limited.
temperatures are improved by no more than 40
C, meanwhile
remarkable deterioration of mechanical properties is commonly
observed. Interestingly, recently enhancement of the thermal
properties and toughness of PVA was synchronously achieved
with a low loading of melamine via hydrogen bond self-
assembly.12 It was demonstrated that Tmax and Tonset of PVA were
increased by 13
C and 16
C, respectively, with only 0.5 wt%
melamine addition; due to the formation of a physically cross-
linked network via H-bonding, the tensile strength and tough-
ness of PVA were improved by 22% and 200%, respectively.
Lignin, the second most abundant biomacromolecule that
exists in the plant kingdom, is relatively inexpensive and widely
available.13 Nevertheless, most lignin is burned as a low cost fuel,
leading to the waste of resources and growing environmental
problems.14 Accordingly, great endeavors have been made to
research its broader applications. Yeo et al. used modied lignin
as a ller in polypropylene composites.15 Binary blends of alka-
line lignin with three poly(vinyl alcohol) samples were investi-
gated.16 Eucalyptus lignosulfonate calcium (HLS)/PVA blends
were researched by Ye, but the compatibility between them was
limited.17 In this work, a gra copolymer of acrylic acid (AA) and
eucalypt lignosulfonate calcium with abundant aromatic struc-
tures and hydroxyl groups was prepared14 and used to improve
the thermal stability of PVA via H-bonding interactions.

a
Polymer Research Institute, Sichuan University, Chengdu 610065, PR China. E-mail:
zhangxi6352@163.com; Fax: +86-028-85402465; Tel: +86-028-85402465 2 Experimental
b
State Key Laboratory of Polymer Material Engineering, Sichuan University, Chengdu 2.1 Materials
610065, PR China
c
School of Materials Science and Engineering, Wuhan Textile University, 430200, PR Poly(vinyl alcohol) (PVA : DP ¼ 1700, degree of hydrolysis 99%)
China was provided by Sichuan Vinylon Factory, SINOPEC (China).

This journal is © The Royal Society of Chemistry 2016 RSC Adv., 2016, 6, 13797–13802 | 13797
 View Article Online

RSC Advances Paper

Eucalyptus lignosulfonate calcium (HLS, 96%) was purchased

from Aladdin (China). Acrylic acid (AA), potassium persulfate
(K2S2O8), absolute ethyl alcohol and hydroquinone were
provided by Kelong Chemicals Co. Ltd. (China).
The gra copolymer (GL) of AA with HLS was prepared using
the same methods as our previous paper14 and the experimental
conditions are shown in Table 1.

2.2 Film preparation

Blend lms were prepared by a solution casting method. A
Published on 26 January 2016. Downloaded by Sichuan University on 9/17/2020 8:05:12 AM.

calculated amount of PVA and GL were dissolved in distilled

water at 90
C for 3 h. The dissolved solution was casted onto
PTFE Petri dishes and dried at 70
C in a vacuum oven for 15 h
to completely eliminate water. The dried lms were named as
GL/PVA and labelled with the prexes 5, 15, 25, 35, 50, which
represent the weight ratio of lignin gra copolymer to the total
sample dry weight. For example, 5GL/PVA represents 5 wt% GL
in the lm (weight is based on the total quantity of dry PVA and
lignin gra copolymer).
2.3 Characterization
Before characterization, except for mechanical tests, all the
samples were dried under vacuum (P < 0.3 MPa) at 105
C for 5 h
to eliminate water.
2.3.1 Fourier-transform infrared (FT-IR) spectroscopy.
FTIR spectra of samples were measured using a FT-IR spectro-
photometer (Nicolet 560) using attenuated total reection. The
measurements were carried out at 4 cm1 resolution with 32
scans in the frequency of range of 4000–650 cm1.
2.3.2 Differential scanning calorimetry (DSC). Glass tran-
sition temperature (Tg) and melting temperature (Tm) of the
blends were determined by using a Mettler Toledo DSC1 (DSC,
Mettler Corp. Switzerland) with a scan rate of 10 K min1 over
a temperature range from 40
C to 300
C. The ow rate of the
nitrogen atmosphere was kept at 50 ml min1 during the
process.
Fig. 1 The FT-IR spectra of PVA, 5GL/PVA, and 15GL/PVA.
(TGA, model SDT Q600). A sample (3–4 mg) was equilibrated at
30
C and then was heated from 30 to 600
C at a heating rate of
10
C min1. The ow rate of the nitrogen atmosphere was
maintained at 100 ml min1 during the whole process.
2.3.6 Mechanical measurements. The tensile strength and
elongation at break of PVA and blend lms were tested at room
temperature using a tensile tester (Instron 5567). Crosshead
speed was set at 20 mm min1. The initial gauge length of the
specimen was 20 mm. The width of each tensile sample is 4
mm. Thicknesses of the lms were measured with a micrometer
in triplicate. The lms were stored at 25
C with RH of 54% for 1
week before testing. The data for each sample was calculated
from the average value of ve specimens. Tensile toughness (Ut)
can be calculated by integrating the area under the tensile
curves, as expressed by following equation.12
X
n
Ut ¼ s3i
i¼0

2.3.3 X-ray diffraction measurements (XRD). X-ray diffrac-
tion patterns were recorded in an angular range of 3–50
(2q) by
using an X’Pert Pro XRD diffractometer equipped with Cu-Ka
radiation operated at 50 kV and 35 mA. The measurements were
performed at a scanning speed of 2q ¼ 0.06
s1.
2.3.4 Scanning electron microscope (SEM). The morphol-
ogies of fracture surfaces were analyzed by SEM (JSM-5900LV) in
order to identify the compatibility between GL and PVA in the
blends. Prior to characterization, blends were immersed in
liquid nitrogen for 3 h to obtain freeze-fractured surfaces.
2.3.5 Thermogravimetric analysis (TGA). The onset (To)
and maximum decomposition (Tmax) temperatures of PVA and
blends were determined using thermal gravimetric analysis
where s and 3 respectively refer to the tensile stress and strain at
failure.
3 Results and discussion
3.1 FTIR analysis
FT-IR spectroscopy is a sensitive tool for monitoring changes in
the interactions of blends.18 The FTIR spectra of PVA and blends
with the addition of lignin gra polymers are illustrated in
Fig. 1. For neat PVA, the wide absorption peak centered at 3313
cm1 is related to the –OH stretching vibration due to the
formation of intermolecular/intramolecular hydrogen bonding.

Table 1 Experimental conditions for grafting reactions of HLS and AA

Sample HLS (g) AA (g) H2O (ml) K2S2O8 (g) Hydroquinone (g) T (
C) Time (min)

GL 1.6 8 18.67 0.24 0.2 50 20

13798 | RSC Adv., 2016, 6, 13797–13802 This journal is © The Royal Society of Chemistry 2016

Paper
Published on 26 January 2016. Downloaded by Sichuan University on 9/17/2020 8:05:12 AM.
Fig. 2 DSC heating thermograms of PVA films as a function of GL content (heating rate ¼ 10 K min1).
Fig. 3 X-ray diffraction patterns of PVA films with different concen-
trations of GL.
Aer blending with the gra polymer from lignin and acrylic
acid, a red shi of –OH peak absorption was observed, sug-
gesting strong interactions between PVA and the lignin gra
Fig. 4 SEM micrographs of GLPVA blend membranes.
This journal is © The Royal Society of Chemistry 2016
View Article Online
RSC Advances
polymer. In 5GL/PVA, this wide –OH absorption band is located
at 3305 cm1, declining by 8 cm1 in comparison with pure
PVA. Upon loading 15 wt% GL, it nally decreased to 3297 cm1,
which can be attributed to the interactions between the –OH
group and carbonyl group from lignin gra polymers. This
hypothesis could be proved by the changes in the absorption
peak of PVA emerging at 1736 cm1 which was assigned to the
typical peak of ester carbonyl (–C]O) structures. With
increasing loading of GL, this peak absorption showed similar
behavior that the –OH band did, shiing gradually from 1736
cm1 to 1728 cm1. This indicates that –C]O groups in PVA
also could form interactions with –OH or –COOH groups of
modied lignin.
3.2 Thermal properties and glass transition temperature
Fig. 2 shows the DSC heating thermograms of PVA lms
according to the concentration of GL. It can be seen that there
were two chain segment motion platforms located at around
80
C and 130
C for pure PVA. Obviously, the former platform
represents the movement of PVA chains in the amorphous
region and the latter platform is mainly caused by the crystal-
line relaxations of PVA.19,20 The pure PVA displayed a Tg of
74.9
C and amorphous GL displayed a Tg of 108.59
C (Fig. 2A).
RSC Adv., 2016, 6, 13797–13802 | 13799

RSC Advances
Published on 26 January 2016. Downloaded by Sichuan University on 9/17/2020 8:05:12 AM.
Fig. 5 Thermal analysis of PVA, GL and GLPVA blending films: (A) TGA curves and (B) DTG curves.
Table 2 Comparison of nano-fillers and GL effect on PVA maximum
decomposition temperature (Tmax)
Enhanced Tmax (
C,
Sample compared with pure PVA)
PVA/graphite oxide 5 wt%31 105
PVA/nano montmorillonite 5 wt%8 40
PVA/graphite oxide 3 wt%9 36
PVA/graphite 3.5 wt%10 20–30
3 wt% GL/PVA 109
Moreover, it can be clearly seen that only one single composi-
tional dependent glass transition temperature (Tg) can be seen
over the entire blend ratio for GL/PVA blends. It can be inter-
preted that the compatibility between GL and PVA is very good
and the system is homogeneous and single phase which is in
accordance with the results of SEM.21,22 Aer GL was incorpo-
rated, Tg was gradually enhanced. For the composite lm with
35 wt% GL, the Tg was increased to 94.1
C with an increment of
19.2
C, compared with pure PVA. This can be ascribed to the
strong hydrogen bonding interactions between GL and PVA,
which can restrict the free movement and arrangement of PVA
chains.12 Besides, the melting point (Tm) gradually decreased as
GL content was increased (from 229
C for pure PVA to 214
C
for 35GL/PVA), which was in accordance with the previous
literature (Fig. 2B).17 The depression of Tm indicates that there
may be strong interactions in the blend system.23,24 Thus, it can
be considered to be GL in the blend system that contributes to
the formation of strong hydrogen bonding with PVA molecules.
3.3 XRD analysis
Within the angular range of 5–40
C, there are two main crys-
talline maxima which may be indexed as 101 at 2q ¼ 19.88
, and
200 at 2q ¼ 22.76
for PVA (Fig. 3). The former crystalline peak,
which is stronger, is oen used for qualitative judgment of the
variation of crystallinity for PVA.25 With rising GL content, this
diffraction peak decreased in intensity indicating that the
ordered arrangement of PVA main chains in the crystalline
region could be disturbed by the incorporation of GL, the
crystallization process of PVA can be suppressed and the crys-
tallinity can decrease.26 It can be inferred that GL/PVA is
13800 | RSC Adv., 2016, 6, 13797–13802
View Article Online
Paper
a compatible system, and there are strong interactions between
GL and PVA. This result is in accordance with our previous
results.
3.4 Scanning electron microscopy
In order to conrm the compatibility of blends, the fracture
surfaces of pure PVA as well as GL/PVA with different compo-
sitions (15GL/PVA and 50GL/PVA) were characterized by SEM
(Fig. 4). Pure PVA shows a very smooth fracture surface. Inter-
estingly, it is noticed that blend lms also show smooth and
homogeneous surfaces even with the incorporation of 50 wt%
GL. GL is homogeneously dispersed in the PVA matrix. As re-
ported for PVA blends with alkali lignin, starch and cellulose
and so on, the aggregation of particles and deteriorated
compatibility are commonly observed due to a lack of strong
interactions.27–29 Our previous studies demonstrated that PVA/
lignosulfonate blends with strong interactions (the q value in
the Kwei equation is 62.4  10.0) still become partly immis-
cible with a 50 wt% addition of lignosulfonate.17 Nevertheless,
the absence of particle aggregation is observed in 50GL/PVA
blend, indicating that the modication of lignosulfonate by
graing is an effective method for improving blend compati-
bility. It could be explained by the fact that the inter-hydrogen
bonding between PVA and lignin is enhanced by adopting this
simple graing method. This good compatibility is obviously
benecial for achieving higher thermal stability and mechan-
ical properties of blends, as proved by later discussions. SEM
micrographs of GLPVA blend membranes.
3.5 Thermogravimetric analysis
TG and DTG curves of pure PVA, GL and GL/PVA blends were
recorded in order to study the effect of lignin gra polymer on
the thermal degradation behavior of PVA (Fig. 5). Interestingly,
the onset decomposition temperature (To) and the maximum
decomposition (Tmax) of PVA were remarkably improved with
the addition of GL. To of pure PVA and GL are 239
C and 217
C,
respectively. By only adding 3 wt% or 5 wt% GL, To and Tmax
were signicantly improved by about 102
C and 109
C,
respectively, compared with pure PVA. With a further increase
of GL, To and Tmax were found to slightly decrease. As reported
in the literature, 5 wt% of nano-montmorillonite improved the
This journal is © The Royal Society of Chemistry 2016

Paper
Published on 26 January 2016. Downloaded by Sichuan University on 9/17/2020 8:05:12 AM.
Fig. 6 (A) Tensile stress–strain curves, (B) tensile strength and Young’s
modulus and (C) elongation at break and tensile toughness at break for
PVA and its blends as a function of GL content.
Tmax of PVA by 40
C and introduction of 3 wt% graphene oxide
also gave the same level of improvement in the Tmax of PVA(36

PVA and it was amazing that the properties of PVA were
C), shown in Table 2.8,9 To the best of our knowledge, GL/PVA
blends show a much better thermal stability compared with any
other results from PVA blends with inorganic or organic llers.
Aer GL is incorporated, it is obvious that the onset decompo-
sition temperature moves to a higher temperature, while the
This journal is © The Royal Society of Chemistry 2016
View Article Online
RSC Advances
melting peak moves to a lower temperature, from the TGA
results together with DSC proles shown in Fig. 2. The
temperature gap between To and Tm was increased, indicating
a new way of thermal processing of PVA. As we all know,
hydroxyl groups take part in the thermal degradation of PVA,
and the stability of hydroxyl groups is crucial for the stabiliza-
tion of PVA.30 A possible explanation for the high thermal
stability of GL/PVA blends is the introduction of aromatic
structures of lignin into PVA chains via strong hydrogen
bonding. Moreover, PVA blends even with high compositions of
GL still showed good compatibility, as proved by SEM and DSC
results. Notably, these functional llers are derived from bio-
based resources which are rather inexpensive and environ-
mentally friendly.
3.6 Mechanical properties
Fig. 6(A)–(C) show the mechanical properties of the blend lms.
Pure PVA displays a tensile strength of 49.90 MPa, Young’s
modulus of 0.71 GPa, elongation at break of 225.85% and
a tensile toughness of 89.86 MJ m3. However, low addition of
GL had signicant effect on the mechanical properties of PVA.
With the incorporation of 5 wt% GL, almost all mechanical
parameters achieved maximum values. The tensile strength and
toughness were increased to 69.15 MPa and 130.19 MJ m3,
respectively, 39% and 45% higher than those of pure PVA.
Meanwhile the elongation at break was slightly deceased to
218.86% and the Young’s modulus was sharply increased to
2.73 GPa. When the GL content reached 15 wt%, the Young’s
modulus achieved the maximum value (3.28 GPa), 362% higher
than that of pure PVA. With a further increase of GL, the
mechanical parameters gradually decreased. At the 35 wt% GL
level, the tensile strength and elongation at break decreased to
44.91 MPa and 125.42%, respectively. But the Young’s modulus
was 196% higher than that of pure PVA. Su et al. reported that
when the mass ratio of alkali and PVA was 2 : 10, the tensile
strength and elongation at break were increased by 20% and
11%, respectively, compared with PVA.27 Ye et al. recently
observed that lignosulfonate (HLS)/PVA blend lms also had
better mechanical properties than pure PVA lm due to the
formation of strong hydrogen bonding and the rigidity of lignin
structures.17 Moreover, adding a small amount of MA can
signicantly improve the strength, modulus, and toughness of
PVA due to the formation of a physically crosslinked network via
H-bond self-assembly.12 Hence, the observed enhancements can
be primarily attributed to the strong hydrogen bonding between
GL and PVA and the rigidness of lignin particles.
4 Conclusion
In this paper, modied lignin (GL) was used as a reinforcer for
considerably changed. GL was homogeneously dispersed in the
PVA matrix and resulted in the enhancement of many proper-
ties. The results of DSC show that only one Tg can be seen over
the entire blend ratio indicating that the blend systems are
homogeneous and miscible. The obtained TGA and DTG results
RSC Adv., 2016, 6, 13797–13802 | 13801

RSC Advances
suggest a very small amount (3% wt) of GL signicantly alters
the thermal properties of PVA and the thermal decomposition
temperature can be higher than that of pure PVA by about 102


C, which was attributed to strong hydrogen bonding. The
mechanical properties of the blend lms were also obviously
improved. With addition of 5 wt% GL, the tensile strength and
Young’s modulus were 39% and 285% higher than those of pure
PVA. Moreover, the tensile toughness was also improved. To
summarize, these results can be attributed to the strong
hydrogen bonding between GL and PVA. This work may open
Published on 26 January 2016. Downloaded by Sichuan University on 9/17/2020 8:05:12 AM.
a door to realize the melt processing of PVA.
References
1 P. Liu, W. Chen, Y. Liu, S. Bai and Q. Wang, Polym. Degrad.
Stab., 2014, 109, 261–269.
2 X. Jiang, T. Jiang, X. Zhang, H. Dai and X. Zhang, Polym. Eng.
Sci., 2012, 52, 2245–2252.
3 J. Jang and D. K. Lee, Polymer, 2003, 44, 8139–8146.
4 W. Wu, H. Tian and A. Xiang, J. Polym. Environ., 2012, 20, 63–
69.
5 A. R. Butt, S. Ejaz, J. C. Baron, M. Ikram and S. Ali, Digest
Journal of Nanomaterials and Biostructures, 2015, 10, 799–809.
6 J. Dodda, P. Bělský, J. Chmelař, T. Remiš, K. Smolná,
M. Tomáš, L. Kullová and J. Kadlec, J. Mater. Sci., 2015, 50,
6477–6490.
7 W. Zhang, X. He, C. Li, X. Zhang, C. Lu, X. Zhang and
Y. Deng, Cellulose, 2014, 21, 485–494.
8 Y.-H. Yu, C.-Y. Lin, J.-M. Yeh and W.-H. Lin, Polymer, 2003,
44, 3553–3560.
9 Y. Xu, W. Hong, H. Bai, C. Li and G. Shi, Carbon, 2009, 47,
3538–3543.
10 X. Yang, L. Li, S. Shang and X.-M. Tao, Polymer, 2010, 51,
3431–3435.
11 S. G. Chaudhri, B. H. Rajai and P. S. Singh, RSC Adv., 2015, 5,
65862–65869.
12 P. A. Song, Z. Xu and Q. Guo, ACS Macro Lett., 2013, 2, 1100–
1104.
13802 | RSC Adv., 2016, 6, 13797–13802
View Article Online
Paper
13 S. Kubo and J. F. Kadla, Biomacromolecules, 2003, 4, 561–567.
14 D. Z. Ye, L. Jiang, C. Ma, M.-H. Zhang and X. Zhang, Int. J.
Biol. Macromol., 2014, 63, 43–48.
15 J.-S. Yeo, D.-W. Seong and S.-H. Hwang, J. Ind. Eng. Chem.,
2015, 31, 80–85.
16 E. Corradini, E. A. G. Pineda and A. A. W. Hechenleitner,
Polym. Degrad. Stab., 1999, 66, 199–208.
17 D.-Z. Ye, L. Jiang, X.-Q. Hu, M.-H. Zhang and X. Zhang, Int. J.
Biol. Macromol., 2016, 83, 209–215.
18 E. Sheha, M. Nasr and M. El-Mansy, Phys. Scr., 2013, 88,
035701.
19 R. M. Hodge, T. J. Bastow, G. H. Edward, G. P. Simon and
A. J. Hill, Macromolecules, 1996, 29, 8137–8143.
20 Y. Nishio and R. S. J. Manley, Macromolecules, 1988, 21,
1270–1277.
21 X. Lu and R. A. Weiss, Macromolecules, 1992, 25, 3242–3246.
22 P. C. Painter, J. F. Graf and M. M. Coleman, Macromolecules,
1991, 24, 5630–5638.
23 C. Sawatari and T. Kondo, Macromolecules, 1999, 32, 1949–
1955.
24 Y. Nishio, T. Haratani, T. Takahashi and R. S. J. Manley,
Macromolecules, 1989, 22, 2547–2549.
25 R. F. Bhajantri, V. Ravindrachary, A. Harisha, V. Crasta,
S. P. Nayak and B. Poojary, Polymer, 2006, 47, 3591–3598.
26 C.-H. Chen, F.-Y. Wang, C.-F. Mao, W.-T. Liao and
C.-D. Hsieh, Int. J. Biol. Macromol., 2008, 43, 37–42.
27 L. Su, Z. Xing, D. Wang, G. Xu, S. Ren and G. Fang,
BioResources, 2013, 8(3), 3532–3543.
28 X. Jiang, H. Li, Y. Luo, Y. Zhao and L. Hou, Int. J. Biol.
Macromol., 2016, 82, 223–230.
29 N. Hameed, R. Xiong, N. Salim and Q. Guo, Cellulose, 2013,
20, 2517–2527.
30 X. Jiang, B. Tan, X. Zhang, D. Ye, H. Dai and X. Zhang, J. Appl.
Polym. Sci., 2012, 125, 697–703.
31 H. J. Salavagione, G. Martinez and M. A. Gomez, J. Mater.
Chem., 2009, 19, 5027–5032.
This journal is © The Royal Society of Chemistry 2016