Accepted Manuscript Title: Development of Regenerated Cellulose/Halloysites Nanocomposites via Ionic Liquids Author: Nurbaiti Abdul Hanid Mat Uzir Wahit Guo Qipeng Shaya Mahmoodian Mohammad Soheilmoghaddam PII: DOI: Reference:
S0144-8617(13)00775-3 http://dx.doi.org/doi:10.1016/j.carbpol.2013.07.080 CARP 7988
To appear in: Received date: Revised date: Accepted date:
6-4-2013 3-7-2013 26-7-2013
Please cite this article as: Hanid, N. A., Wahit, M. U., Qipeng, G., Mahmoodian, S., & Soheilmoghaddam, M., Development of Regenerated Cellulose/Halloysites Nanocomposites via Ionic Liquids, Carbohydrate Polymers (2013), http://dx.doi.org/10.1016/j.carbpol.2013.07.080 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
1 1
Development of Regenerated Cellulose/Halloysites Nanocomposites via Ionic Liquids
2 3
Nurbaiti Abdul Hanida, Mat Uzir Wahitb*, Guo Qipengc, Shaya Mahmoodiana, Mohammad Soheilmoghaddama
4
a
Department of Polymer Engineering, Faculty of Chemical Engineering, 81310 Universiti Teknologi Malaysia,
5 6 c
Center for Composites, 81310 Universiti Teknologi Malaysia, Johor, Malaysia
Polymers Research Group, Institute for Frontier Materials, Deakin University, Geelong, Victoria 3216,
8
Australia *Corresponding author: [email protected]
us
9
cr
7
b
ip t
Johor, Malaysia
Center for Composites, Universiti Teknologi Malaysia (UTM), 81310 Skudai, Johor, Malaysia.
11
Tel.: +607 553 5909; fax: +607 553 6165
an
10
12
Abstract
M
13 14
In this study, regenerated cellulose/halloysites (RC/HNT) nanocomposites with different
16
nanofillers
17
methylimidazolium chloride (EMIMCl) ionic liquid. The films were prepared via solution
18
casting method and were characterized by X-ray diffraction (XRD), scanning electron
19
microscopy (SEM) and transmission electron microscopy (TEM). The mechanical properties
20
were investigated by tensile testing. It clearly displayed a good enhancement of both tensile
21
strength and Young’s modulus with HNT loading up to 5wt %. As the HNT loadings
22
increased to 5wt%, the thermal behaviour and water resistance rate was also increased. The
23
TEM and SEM images also depicted even dispersion of the HNT and a good inter tubular
24
interaction between the HNT and the cellulose matrix.
fabricated
te
were
by
dissolving
the
cellulose
in
1-ethyl-3-
Ac ce p
loading
d
15
25 26
Keywords: Regenerated cellulose, ionic liquid, EMIMCl, halloysites, nanocomposites
27
Page 1 of 26
2 28
1.
Introduction
29
Recently, the development of natural biopolymer materials has received enormous
31
interest as a substitute for non-biodegradable petroleum based plastics. Biopolymer materials
32
are polymers that are biodegradable. The input materials for the production of these polymers
33
may be either renewable or synthetic. There are four main types of biopolymer including
34
starch, sugar, cellulose and synthetic materials. Current and future developments in
35
biodegradable polymers and renewable materials focus mainly on the improvement of product
36
properties but not as an alternative solution to the insecurity of petroleum supplies or to
37
reduce the environmental threat (Wu, et al., 2009). Besides being available on a sustainable
38
basis, biopolymer materials have several economic and environmental advantages due to their
39
low cost, availability from renewable sources and their ability to replace some synthetic
40
polymers (Tang et al., 2012).
cr
us
an
M
d te
41
ip t
30
Cellulose was used in this study because it is the most abundant natural polymer on
43
earth and can easily be obtained from wood pulp and cotton. Cellulose has excellent
44
mechanical properties and thermal performance (Nishino, Matsuda and Hirao, 2004).
45
Cellulose is an important renewable resource and is regaining importance as renewable
46
chemical resources to replace petroleum-based materials (Ma et al., 2011; Delhom et al.,
47
2010). Therefore, effective utilization of cellulose not only reduces the consumption of our
48
limited fossil resources but also protects the environment. Nowadays, ‘green’ composites
49
have grabbed a lot of attention because of their unique properties such as outstanding
50
transparency, mechanical properties, non-toxicity and also high biodegradability rate (Takagi
51
and Asano, 2008). However, there were difficulties in processing and regenerating the
52
cellulose as cellulose has a hydrogen bond and a partially crystalline structure which are the
Ac ce p
42
Page 2 of 26
3 53
main obstructions for dissolving or regenerating cellulose in conventional solvent (Cao et al.,
54
2009).
55
Recently, ionic liquids (ILs), a new class of ‘green’ solvent have drawn much attention
57
due to their distinctive properties such as non-volatility, non-flammability, chemical and
58
thermal stability and ease of recycling (Heinze, et al., 2005; Feng and Chen, 2008). Although
59
there are a wide range of ILs, 1-ethyl-3-methylinidazolium chloride (EMIMCl), a molten salt
60
which exists as a liquid at relatively low temperature (
S0144-8617(13)00775-3 http://dx.doi.org/doi:10.1016/j.carbpol.2013.07.080 CARP 7988
To appear in: Received date: Revised date: Accepted date:
6-4-2013 3-7-2013 26-7-2013
Please cite this article as: Hanid, N. A., Wahit, M. U., Qipeng, G., Mahmoodian, S., & Soheilmoghaddam, M., Development of Regenerated Cellulose/Halloysites Nanocomposites via Ionic Liquids, Carbohydrate Polymers (2013), http://dx.doi.org/10.1016/j.carbpol.2013.07.080 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
1 1
Development of Regenerated Cellulose/Halloysites Nanocomposites via Ionic Liquids
2 3
Nurbaiti Abdul Hanida, Mat Uzir Wahitb*, Guo Qipengc, Shaya Mahmoodiana, Mohammad Soheilmoghaddama
4
a
Department of Polymer Engineering, Faculty of Chemical Engineering, 81310 Universiti Teknologi Malaysia,
5 6 c
Center for Composites, 81310 Universiti Teknologi Malaysia, Johor, Malaysia
Polymers Research Group, Institute for Frontier Materials, Deakin University, Geelong, Victoria 3216,
8
Australia *Corresponding author: [email protected]
us
9
cr
7
b
ip t
Johor, Malaysia
Center for Composites, Universiti Teknologi Malaysia (UTM), 81310 Skudai, Johor, Malaysia.
11
Tel.: +607 553 5909; fax: +607 553 6165
an
10
12
Abstract
M
13 14
In this study, regenerated cellulose/halloysites (RC/HNT) nanocomposites with different
16
nanofillers
17
methylimidazolium chloride (EMIMCl) ionic liquid. The films were prepared via solution
18
casting method and were characterized by X-ray diffraction (XRD), scanning electron
19
microscopy (SEM) and transmission electron microscopy (TEM). The mechanical properties
20
were investigated by tensile testing. It clearly displayed a good enhancement of both tensile
21
strength and Young’s modulus with HNT loading up to 5wt %. As the HNT loadings
22
increased to 5wt%, the thermal behaviour and water resistance rate was also increased. The
23
TEM and SEM images also depicted even dispersion of the HNT and a good inter tubular
24
interaction between the HNT and the cellulose matrix.
fabricated
te
were
by
dissolving
the
cellulose
in
1-ethyl-3-
Ac ce p
loading
d
15
25 26
Keywords: Regenerated cellulose, ionic liquid, EMIMCl, halloysites, nanocomposites
27
Page 1 of 26
2 28
1.
Introduction
29
Recently, the development of natural biopolymer materials has received enormous
31
interest as a substitute for non-biodegradable petroleum based plastics. Biopolymer materials
32
are polymers that are biodegradable. The input materials for the production of these polymers
33
may be either renewable or synthetic. There are four main types of biopolymer including
34
starch, sugar, cellulose and synthetic materials. Current and future developments in
35
biodegradable polymers and renewable materials focus mainly on the improvement of product
36
properties but not as an alternative solution to the insecurity of petroleum supplies or to
37
reduce the environmental threat (Wu, et al., 2009). Besides being available on a sustainable
38
basis, biopolymer materials have several economic and environmental advantages due to their
39
low cost, availability from renewable sources and their ability to replace some synthetic
40
polymers (Tang et al., 2012).
cr
us
an
M
d te
41
ip t
30
Cellulose was used in this study because it is the most abundant natural polymer on
43
earth and can easily be obtained from wood pulp and cotton. Cellulose has excellent
44
mechanical properties and thermal performance (Nishino, Matsuda and Hirao, 2004).
45
Cellulose is an important renewable resource and is regaining importance as renewable
46
chemical resources to replace petroleum-based materials (Ma et al., 2011; Delhom et al.,
47
2010). Therefore, effective utilization of cellulose not only reduces the consumption of our
48
limited fossil resources but also protects the environment. Nowadays, ‘green’ composites
49
have grabbed a lot of attention because of their unique properties such as outstanding
50
transparency, mechanical properties, non-toxicity and also high biodegradability rate (Takagi
51
and Asano, 2008). However, there were difficulties in processing and regenerating the
52
cellulose as cellulose has a hydrogen bond and a partially crystalline structure which are the
Ac ce p
42
Page 2 of 26
3 53
main obstructions for dissolving or regenerating cellulose in conventional solvent (Cao et al.,
54
2009).
55
Recently, ionic liquids (ILs), a new class of ‘green’ solvent have drawn much attention
57
due to their distinctive properties such as non-volatility, non-flammability, chemical and
58
thermal stability and ease of recycling (Heinze, et al., 2005; Feng and Chen, 2008). Although
59
there are a wide range of ILs, 1-ethyl-3-methylinidazolium chloride (EMIMCl), a molten salt
60
which exists as a liquid at relatively low temperature (
