Beruflich Dokumente
Kultur Dokumente
Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa
Review
Wood Biology and Wood Products, Burckhardt-Institute, Georg August University of Gttingen, Bsgenweg 4, D37077 Gttingen, Germany
Centre for Timber Engineering, School of Engineering and the Built Environment, Edinburgh Napier University, 10 Colinton Road, EH10 5DT Edinburgh, United Kingdom
a r t i c l e
i n f o
Article history:
Received 9 November 2009
Received in revised form 4 March 2010
Accepted 4 March 2010
Keywords:
A. Silane coupling agents
A. Fibres
B. Fiber/matrix bond
B. Environmental degradation
a b s t r a c t
Natural fiber reinforced polymer composites (NFPCs) provide the customers with more alternatives in the
material market due to their unique advantages. Poor fibermatrix interfacial adhesion may, however,
negatively affect the physical and mechanical properties of the resulting composites due to the surface
incompatibility between hydrophilic natural fibers and non-polar polymers (thermoplastics and thermosets). A variety of silanes (mostly trialkoxysilanes) have been applied as coupling agents in the NFPCs to
promote interfacial adhesion and improve the properties of composites. This paper reviews the recent
progress in using silane coupling agents for NFPCs, summarizes the effective silane structures from the
silane family, clarifies the interaction mechanisms between natural fibers and polymer matrices, and presents the effects of silane treatments on the mechanical and outdoor performance of the resulting
composites.
Crown Copyright 2010 Published by Elsevier Ltd. All rights reserved.
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doi:10.1016/j.compositesa.2010.03.005
matrices; however, the resulting composites, similar to the composites with non-polar matrices, will be susceptible to moisture
deterioration and fungal damage during outdoor service. The moisture absorption of the natural fibers may cause dimensional
changes of the resulting composites and weaken the interfacial
adhesion [19,20]. Mould and decay fungi may also grow on/in
the composites, although more slowly than in the fibers alone,
when they are utilized in the long-term under wet conditions
[21]. In addition, natural fibers are of limited thermal stability
and, therefore, thermal degradation may take place during composite processing at a high temperature, especially in the cases of
thermal extrusion and hot compression processes.
By this token, treatment of natural fibers is beneficial in order to
improve the water resistance of fibers, enhance the wettability of
the natural fiber surface by polymers (mainly non-polar polymers)
and promote interfacial adhesion. The performance of fibers is critical to obtain the improved physical and mechanical properties of
the resulting composites. Physical treatments (e.g. electronic discharge in the different media such as plasma and corona technologies [2225]) may create a hydrophilic or hydrophobic fiber
surface by changing the surface energy to consequently increase
the compatibility of the treated fiber with the polymer matrices.
These surface treatments only modify a very shallow surface of cell
walls and thus do not change the hygroscopic characteristics of fibers. Chemical modification provides the means of permanently
altering the nature of fiber cell walls [26]: by grafting polymers
onto the fibers [27,28], crosslinking of the fiber cell walls [29], or
by using coupling agents [4]. These modifying strategies have been
generally reviewed recently [26,30]. The chemical modification
may make the fiber cell walls more dimensionally stable, reduce
water sorption, or increase resistance against fungal decay, but
there may be an associated reduced dynamic strength such as impact strength due to embrittlement. A coupling agent is a chemical
that functions at the interface to create a chemical bridge between
the reinforcement and matrix. It improves the interfacial adhesion
when one end of the molecule is tethered to the reinforcement surface and the functionality at the other end reacts with the polymer
phase. Extensively used coupling agents for NFPCs are copolymers
containing maleic anhydride such as maleated polypropylene
(MAPP) or maleated polyethylene (MAPE) [18,3133]. The anhydride groups of the copolymers may react with the surface hydroxyl groups of natural fibers forming ester bonds whilst the other
end of copolymer entangles with the polymer matrix due to their
similar polarities [34]. Isocyanates have also been reported as the
coupling agents used in NFPCs. Urethane links can be formed between the isocyanate functionality and the hydroxyl group of natural fibers [35,36], consequently blocking these hygroscopic
hydroxyl sites [37].
Silanes are recognized as efficient coupling agents extensively
used in composites and adhesive formulations [38]. They have
been successfully applied in inorganic filler reinforced polymer
composites such as glass fiber reinforced polymer composites
[e.g. 39,40] and mineral filled polymer composites [e.g. 41,42]. Silanes are also adhesion promoters in many adhesive formulations
or are used as substrate primers, giving stronger adhesion [43]. The
bifunctional structures of silanes have also been of interest in
applying them for natural fiber/polymer composites, since both
glass fibers and natural fibers bear reactive hydroxyl groups, and
extensive researches have accordingly been carried out to screen
the varied silane structures for NFPC production.
The aim of this paper is to review the recent progress in using
silane coupling agents for the production of natural fiber reinforced
polymer composites. The effects of treatments of natural fibers
with silanes on the properties of fibers and the resulting composites are discussed and the interaction mechanisms between phases
clarified.
807
808
Table 1
Silanes used for the natural fiber/polymer composites: chemical structures, organofunctionalities and target polymer matrices.
a
b
Structure
Functionality
Abbreviation
Target matrix
References
(RO)3SiA(CH2)3ANH2a
Amino
APS
Epoxy
Polyethylene
Butyl rubber
Polyacrylate
PVC
[19,4447]
(RO)3SiACH@CH2
Vinyl
VTS
Polyethylene
Polypropylene
Polyacrylate
[44,4852]
(RO)3SiA(CH2)3AOOC(CH3)C@CH2
Methacryl
MPS
Polyethylene
Polyester
[20,44,53,54]
(RO)3SiA(CH2)3ASH
Mercapto
MRPS
Natural rubber
PVC
[53,5557]
(RO)3SiA(CH2)3AOACH2CHCH2O
Glycidoxy
GPS
Epoxy
Butyl rubber
Polysulfide
[19,45,58,59]
R2ASiACl2
Chlorine
DCS
Polyethylene
PVC
[47,60]
Vinyl
VSPP
VSPE
Polypropylene
Polyethylene
[52,61]
(RO)3ASiAR00 AN3b
Azide
ATS
Polypropylene
Polyethylene
Polystyrene
[6264]
(RO)3SiA(CH2)15CH3
Alkyl
HDS
Polyethylene
Natural rubber
[53,65,66]
R = Amethyl or ethyl.
R00 = AC6H4ASO2A.
silanes; however, additional water is required to achieve a complete hydrolysis of silanes [7072].
OR
(a)
RO
Si
CH2
OR
OR
(b)
RO
Si
(CH2 )3
OR
CH2
R1(O)
(c)
R1O
R1(O)
Si
R2
R2
Fig. 1. Different length of the bridge connecting the silicon atom and functionalities: a-silane having a methylene spacer (a), c-silane bearing a propylene spacer
(b), and the schematic diagram of the a-effect in the aminomethylene silane (c)
[75].
809
affected by the hydrolysis condition used such as the solvent, temperature, pH, concentration of silanes [7678]. Under optimum
conditions hydrolysis may be accelerated, but condensation of silanols is inhibited to maintain a stable intermediary structures such
as silanol monomer or dimers [76,79,80].
The dynamics of the hydrolysis and ensuing condensation of
several trimethoxysilanes bearing different chain length of alkyl
functionalities (methyl, ethyl, propyl, or butyl) have been investigated in wateracetone mixtures by quantifying the produced
methanol using internal reflection Fourier transform infrared spectroscopy (FTIR) combined with statistical regression. The results
show that the relative rates of the consecutive hydrolysis reactions
and the rate of condensation to form siloxane bonds depend on the
silane organofunctionalities, and this FTIR technique permits the
tailoring of the composition of the alkoxysilane compounds in
solution to obtain the desired rate and degree of hydrolysis of alkoxy groups, and the extent of siloxane bond formation [82]. The
hydrolysis rates of APS, c-diethylenetriaminopropyl trimethoxy silane (TAS) and MPS were established using 1H NMR by measuring
the evolution of liberated free alcohol, and it showed that the rate
increased in the order MPS < APS < TAS. The formation of the silanol groups was followed by their condensation to generate oligomeric structures. Whereas APS and MPS only gave soluble
products, colloidal particles by contrast precipitated in the medium when the TAS was hydrolyzed [83,84]. At alkaline pH, the alkoxy groups of APS were hydrolyzed almost immediately in water
and the resulting aminosilanols formed a cyclic structure with an
internal hydrogen-bonded ring (Fig. 2). Bonding of the silanol
hydrogen makes the silanol stable against condensation in the concentrated aqueous solutions. As a result, there was no insoluble gel
in an alkaline aqueous solution of the aminoalkylsilanes after several months of storage [43]. In the pH range of 36, aminosilanol
groups in the solution were relatively more stable, existing as zwitterionic structures [43]. In contrast, MPS hydrolyzes much slower
and requires the use of an amine as catalyst in the water/solvent
solution [83].
Generally, under acid-catalyzed conditions, the hydrolysis rate
of silanes forming silanol groups is greater than the condensation
rate of the ensuing silanols forming siloxane bonds [72,79]. These
competing reactions of hydrolysis and condensation in an ethanol/water (80/20, w/w) solution at different pH values were ascertained in situ using 1H, 13C, and 29Si NMR spectroscopy [72]. After
hydrolysis of the silane, the ensuing silanol groups gradually selfcondensed into the structures of dimer (T1) (Fig. 3a), linear siloxane
(T2) (Fig. 3b), and ultimately rigidly three-dimensional polysiloxane cage structures (T3) (Fig. 3c). In an acidic solution, the hydrolysis rate of MPS was accelerated and the self-condensation rate was
reduced compared to those in the alkaline solution. The entities
with T3 units appeared after more than 1 month under acidic conditions; however, they appeared after only 6 h in the alkaline solution. The formation of a T3 structure in the treating solution must
be inhibited since this may reduce the number of silanol groups
adsorbed to fibers. The silanol condensation will also make the cell
wall penetration by silane impossible due to the increased molecular size.
CH2CH2
CH2
Si
O
OH
NH2
R'
OR
Si
Si
OR
RO
(a)
RO
R'
T1
structure
dimer or chain end
R'
(b)
OR
RO
R'
R'
Si
RO
Si
O
OR
Si
OR
T2 structure
linear link
R'
R'
R'
Si
Si
Si
RO
(c)
RO
OR
O
OR
O
Si
RO
OR
R'
T3 structure
three dimensional
R' = functional group; R = alkyl group
Fig. 3. Schematic presentation of Ti silane structures [72].
810
matrices [52]. Through this method of application, the alkoxysilanes do not undergo any hydrolysis.
Impregnation processes where natural fibers were treated with
prehydrolyzed silane solution to allow the silane penetrate into the
fiber lumina and further diffuse into the cell walls have been reported [85,86]. Consequently, both fiber surfaces and cell walls
are modified with silanes (bulking treatment). The penetration of
silanes into cell walls is influenced by the molecular size of silane
which is influenced by the aging of the hydrolyzed silane solution.
Improper hydrolysis processes may result in a fast condensation of
silanols thereby prematurely increasing the molecular size of the
silanes. In this case diffusion of silanes into the cell walls will be
limited or prevented entirely. The bulking treatment of fiber cell
walls can change the properties of cell walls, and as a result promote the performance improvement of the ensuing composites.
Compared to the surface treatment such as spraying, the impregnation process may cause problems for some type of fibers. For
example, fine short fibers may aggregate and cannot thus evenly
disperse in the solution; the drying process may also consume
energy.
3.2. Interaction mechanisms between silanes and natural fibers
3.2.1. Adsorption between silanols and hydroxyl groups of fibers
When hydrolyzed silane solutions are mixed with natural fibers,
the reactive silanol groups have a high affinity for each other, forming ASiAOASiA bonds and also for the hydroxyl sites of fibers via
hydrogen bonds. The adsorption isotherms of silanol groups onto
cellulose fiber surfaces have been established using the techniques
of FTIR and UV spectroscopy [87]. The silanols of APS, TAS, or MPS
firstly form a monolayer on the fiber, and then are further adsorbed
due to the temperature-driven condensation reaction, which results in the formation of a rigid polysiloxane layer on the fiber surface. The polysiloxane layer on the fiber surfaces may hinder any
diffusion of the silane molecules into the cell walls, or result in a
concentration gradient in the cell walls. Consequently, the hydrolysis conditions such as pH of solution have to be adjusted to slow
down the condensation thereby allowing the reactive silanol access to hydroxyl sites in the fiber cell walls. Both, APS and TAS, displayed higher adsorption towards the surfaces of cellulose fibers
than did MPS, since the former two may establish strong hydrogen
bonds between the amino groups and the fiber hydroxyl groups.
Owing to steric hindrance by the aromatic ring, c-phenyl-aminopropyltrimethoxy silane (PAPS) shows the lowest adsorption affinity for cellulose fibers compared to APS, TAS, and MPS. The
adsorption of silanols in the fiber cell walls is not clear in the case
of bulking treatments (impregnation treatment) due to the difficulties of in situ determination; however, the affinity of silanols for
the microfibrils of the cell walls may be similar to that displayed
with the fiber surface. To fully modify the cell walls, the silanol
monomers or oligomers have to be small enough to get access to
the hydroxyl groups of the interior of the cell walls.
3.2.2. Bonding of silanols and the hydroxyl groups of fibers
The free silanol groups may undergo further condensation
forming ASiAOASiA network linkages on/in the fibers during solvent evaporation as evidenced by 29Si NMR study [72]. Unlike the
SiAOAC bonds, the ASiAOASiA bonds formed are very stable towards hydrolysis [43]. The hydrogen bonds formed between the
adsorbed silanols and hydroxyl groups of natural fibers at the
adsorption sites do not, however, convert into the covalent bonds
of ASiAOACA linkages at room temperature [8890], and thus
the adsorbed silanes may be leached off the fibers by Soxhlet
extraction with ethanol [87]. Heating (e.g. 110 C for 2 h) may remove the water or solvents in the fibers and drive the dehydration
reaction at the adsorption sites between silanols and fiber hydroxyl
groups thereby forming ASiAOACA bonds [69,87,91]. Further evidence on the interfacial bonds of silane-modified cellulose fibers
measured using X-ray photoelectron spectroscopy (XPS) and FTIR
spectroscopy confirm the occurrence of ASiAOACA bonds
[87,9294]. Heating also promotes the condensation of free silanol
groups resultantly forming the solid polysiloxane layers on the fiber surface and the entangled polysiloxane networks in the cell
walls. Hydrogen bonding is also possible between the ASiAOASiA
backbone and the hydroxyl groups of fibers. In the case of a bulking
treatment, the polysiloxane networks in the cell walls may reduce
the size of the cell wall nano-pores where the water is normally
able to gain access. As a result, the water sorption of the cell walls
may be reduced. In addition, the aminosilanes such as APS may
form the strong intra- and inter-molecular hydrogen bonds with
its amino group also possessing a strong affinity towards the hydroxyl groups of fibers. These interactions in the aminosilane-treated fibers may result in the formation of a cage-like structure in the
fibers [44,95]. However, it must be emphasized that the bonds of
ASiAOACA are not stable towards hydrolysis under a moist environment. Hydrolysis of ASiAOACA bonds will produce the free silanol groups again. The reproduced silanols may condense
themselves or form ASiAOACA bonds again under heating
conditions.
In general, interaction of silane coupling agents with natural fibers may mainly proceed through following steps [72,96]:
(1) Hydrolysis (Fig. 4a): The silane monomers are hydrolyzed in
the presence of water and catalyst (normally acid or base)
liberating alcohol and yielding reactive silanol groups.
(2) Self-condensation (Fig. 4b): During the hydrolysis process,
the concomitant condensation of silanols (aging) also takes
place. The condensation should be minimized at this stage
to leave the silanols free for being adsorbed to the hydroxyl
groups in the natural fibers. For the bulking treatment of
fibers, the condensation should also be controlled in order
to retain a small molecular size of monomers or oligomers
to diffuse into the cell walls. The condensation rate of silanols is controllable by adjusting the pH of the hydrolysis system. An acidic pH environment is usually preferable to
accelerate the hydrolysis rate of silanes but slow down the
condensation rate of silanols.
(3) Adsorption (Fig. 4c): The reactive silanol monomers or oligomers are physically adsorbed to hydroxyl groups of natural
fibers by hydrogen bonds on the fiber surfaces (surface coating) and/or in the cell walls (cell wall bulking), which
depends on the molecular size of silanol monomers/oligomers formed. The free silanols also adsorb and react with
each other thereby forming a rigid polysiloxane structures
linked with a stable ASiAOASiA bond.
(4) Grafting (Fig. 4d): Under heating conditions, the hydrogen
bonds between the silanols and the hydroxyl groups of fibers
can be converted into the covalent ASiAOACA bonds and
liberating water. The residual silanol groups in the fibers will
further condense with each other. The bonds of ASiAOACA
may not be stable towards hydrolysis; however, this bond is
reversible when the water is removed at a raised
temperature.
3.3. Effect of silane treatments on the fiber properties
3.3.1. Stabilization against hydrolysis
Although the SiAOAC bond is not stable towards hydrolysis
[43], several authors have found that the silanes in the treated fibers or wood are nonetheless resistant against water leaching
[85,87,97]. Commercial microcrystalline cellulosic fibers treated
with MPS, APS, and TAS silanes only had slight weight loss after
811
(a) Hydrolysis:
R'
Si
OH
H or OH
+ 3 H2O
OR
R'
Si
OR
R'
Si
OH
OH
OH
(b) Self-condensation:
+ 3 ROH
OH
OH
+ HO Si
OH
R' Si
R'
OH
OH
OH
O
R'
Si
R'
+ H2O
OH
Si
Si
O
R'
OH
O
R'
+ x H2O
Si
Si
R'
O
OH
OH
O
HO Si
R'
HO
Si
R'
H
OH
(c) Adsorption:
OH
OH
HO
Si
OH
O
Si
OH
R'
HO
Si
OH
O
Si
R'
H
R'
OH
R'
OH
OH
HO
Si
R'
H
OH
Si
R'
O
OH
O
HO
Si
OH
O
Si
H
R'
OH
R'
Si
R'
Si
+ x H2O
R'
15 h Soxhlet extraction with ethanol [87]. Donath et al. [97] determined the anti-leaching ability of wood treated with the oligomers
of methyl- and propyl-triethoxysilane and a multifunctional aqueous siloxane HS 2909 (with the functionalities of alkyl and amino
groups). Both silane oligomers, especially the latter, cannot be leached out of pine wood after treatment. Both silanes MPS and vinyltrimethoxy silane (VTS) can penetrate into and react with the cell
walls of Corsican pine (Pinus nigra) sapwood via radical grafting or
condense in the cell walls [85]. After five leaching cycles involving
water saturation followed by oven drying, only small amounts of
silane were leached out and the treated wood still maintained a
high anti-swelling efficiency (ASE), indicating the silanes still bond
to cell walls after leaching. The high efficiency in resisting water
leaching may be apparently attributed to the highly hydrophobic
alkyl groups and/or high affinity of silanols for cellulosic hydroxyl
groups. In case of aminosilane, the strong affinity of amino groups
for the hydroxyl groups of fibers should be also considered as a reason. In addition, X-ray mapping (SEM-EDX) of silane treated wood
reveals an accumulation of silicon in the cell lumina and bordered
pits thereby plugging of these typical penetration pathways for
water [97]. Where polymerization occurs within the cell wall, the
silane polymers become entangled with the cell wall polymeric
network and are leach-resistant.
3.3.2. Hydrophobation of fibers
By a proper surface and/or bulking treatment with silanes, the
normally hygroscopic natural fibers can be converted into a hydrophobic reinforcement for non-polar polymer matrices. A surface
coating only decreases the water sorption rate and does not sub-
812
Table 2
Effect of silane treatment on mechanical properties of coir fibers [103].
Treatment
Time
(h)
Tenacity (g/
denier)
Elongation at
break (%)
Untreated
2% MPS
0.5%
DMVS
0.5%
DMVS
Benzene
1.00
0.50
2.26
1.82
1.47
28.80
23.52
22.44
38.30
36.09
30.13
0.25
1.80
26.12
34.20
1.00
1.71
23.72
35.94
813
Fiber (%)
Polymer
Improvement (%)
Tensile
strength
VTS (4)
MPS (4)
APS (4)
MPS (2)
HDS (3)
MRPS (3)
APS (0.01)
DCS (0.1)
a
Immersion in ethanol/water
Immersion in ethanol/water
Immersion in p-xylene
Spray with aqueous solution
Immersion in ethanol/water
Immersion in ethanol/water
Immersion in acetone
Dry blending
CTMP (40)
CTMP (40)
CTMP (30)
Wheat straw fiber
Cellulosic fibers
Cellulosic fibers
Pine TMP (10)a
Newsprint fiber (45)
LDPE
LDPE
PS
PP
LDPE
LDPE
PE
PVC
27
9
6
2
6
12
1
5
References
Tensile
modulus
65
74
25
10
7
6
15
Elongation at break
Energy at yield
107
245
18
6
30
16
25
19
[105]
[105]
[44]
[112]
[53]
[53]
[47]
[47]
O
Si (CH2) 3
O
NH2
Cl
O
Si (CH2)3
O
Cl
NH
PVC
Fig. 5. Acidbase reaction between APS-modified fibers and PVC matrix [47].
molecules in a similar fashion to propagate the free radical reaction. A previous study showed, however, that VTS did not homopolymerize during reaction due to its bulky silane side groups
[117]. Accordingly, the radical reaction would ultimately result
in a grafting of vinylsilane onto thermoplastics as shown in
Fig. 6 [44,118]. The grafting of vinylsilanes onto thermoplastic
matrices has two options: one approach is to graft vinylsilanes
onto matrices with the resulting copolymer being used as a coupling agent to bond the natural fiber and matrices; the other way
is to treat the fiber with the vinylsilane solution and the grafting
reaction appears in the thermal compounding process of vinylsilane treated fibers and thermoplastic matrices.
CH 2
CH 2
R-O-O-R
CH 2
HC
CH 2
CH 2
PE chain
PE radical
OR
OC 2 H 5
R-O-O-R
H2C
CH
Si
OC 2 H 5
CH 2
. CH
OC 2 H 5
Si
OC 2 H 5
OC 2 H 5
OC 2 H 5
OR
OR
CH 2
HC
CH 2
CH 2
+
. CH
OC 2 H 5
Si
OC 2 H 5
OC 2 H 5
CH 2 CH 2
OC 2 H 5
Grafting
HC
CH 2
CH
Si
OC 2 H 5
OC 2 H 5
814
Table 4
Mechanical properties of natural fiber/thermoplastic composites coupled with the representative vinylsilanes in the presence of peroxide initiator.
Components of composite
Fiber (%)
Polymer
Silane (%)
Initiator (%)
Henequen (20)
CTMP of aspen (30)
Wood flour (40)
HDPE
LDPE
HDPE
VTS (1)
MPS (4)
VTS (2)
DCUP (0.5)
DCUP (unclear)
DCUP (0.17)
Flax (30)
CTMP of aspen (30)
CTMP of spruce and balsam fir (20)
PP
LDPE
PVC
MPS (3)
VTS (4)
MRPS (2)
DCUP (0.3)
DCUP (unclear)
BPO (0.8)
References
[91,94,124]
[51]
[50,121,122]
OR
RO
Si
[106]
[51]
[57]
O
R'
OR
N3
OR
OH
RO Si
OR
R"
N3
OR
OR
O
Si
N3
OR
Si
OR
R"
N3
OR
R"
OR
Si
OR
R"
N:
Si
R"
N:
N2
R"
NH
OR
CH2
CH2
n
OR
O
Si
OR
CH
CH2
n
4.1.2.2. Grafting reaction between the silane-treated fiber and matrices. A study of the melt rheological behavior showed that treatment of pineapple fibers with VTS (4.0 wt.% of fiber) and
peroxide DCUP (2.0 wt.% of fiber) caused an increase in the melt
viscosity of the resulting LDPE composites. This was attributed to
the increased fibermatrix interfacial interaction due to a grafting
reaction. Treatment of pineapple fibers with the peroxides DCUP
(0.5 wt.% of LDPE) or BOP (1.0 wt.% of LDPE) alone also increased
the melt viscosity of resulting LDPE composites due to the free radical grafting reaction between fibers and LDPE at a high temperature (125145 C) [49]. The grafting reaction of VTS-treated wood
flour with PE in the presence of DCUP initiator caused a significant
increase in the flexural strength (up to 87%) and impact strength
(more than 100%) of the resulting extruded composites
[50,121,122]. The reported effects of grafting vinylsilanes with different thermoplastic matrices on the mechanical properties of
resulting NFPCs are exemplified in Table 4.
Grafting effects of vinylsilane on the mechanical properties of
the resulting NFPCs depended on the types of thermoplastic matrices [123,124]. Treatment of fibers with VTS or MPS in the presence
of DCUP initiator resulted in an increase of up to 62% in the tensile
strength of the PE matrix composites [51]; however, incorporation
of fibers with the same treatment into a polystyrene matrix did not
substantially improve the mechanical properties of the ensuing
composites compared to the untreated fiber reinforced composites
[44]. It may be concluded that the proper match of silane organofunctionality with the target polymer matrices is important to attain a desired coupling effect (Table 1).
Azidosilanes with a general formula (CH3O)3SiAR0 ASO2N3
(Fig. 7) have been reported to be highly efficient in coupling mineral fillers with polyolefin matrices [6264,125]. Azidosilanes can
also be hydrolyzed thereby forming the reactive silanols which
are able to react with or condense in the fibers. The organofunc-
815
OH
O
n
Fig. 9. Molecular structure of epoxy pre-polymer diglycidyl ethers of bisphenol A
(DGEBA).
the amine-epoxy reaction [46]. The interfacial interactions of DGEBA and silanes were studied by incorporating the polysiloxane
powders formed from condensation of hydrolyzed APS into DGEBA
matrix [108,132]. FTIR evidence showed that the epoxy resin reacted with polyaminosiloxane forming covalent bonds at the interface [132]. Use of a polymerizing accelerator benzyl
dimethylamine (BDMA) increased the reaction rate of the epoxy
resin and polyaminosiloxane. The coupling mechanism of aminosilanes in the fiber/epoxy composites have been proposed by several authors as summarized in Fig. 10 [e.g. 45,46,108,132].
Treatments of flax fibers with APS resulted in an enhancement of
tensile strength up to 17%, and of the modulus up to 25%, but did
not change the impact toughness of the resulting epoxy composites [133]. Sisal fiber/epoxy composites (40 vol.% of fiber) coupled
with 5% APS showed a considerable improvement in the compression strength and wet tensile strength [19].
4.2.2. Reaction with polyester resin
The vinylsilanes have been demonstrated to be able to efficiently couple natural fibers and unsaturated polyester (UP) resins.
A dominant co-polymerization mechanism is proposed where the
methacrylic or vinyl group in the silanes is capable of reacting with
the double bonds of the UP matrix when the mixture system is initiated by a peroxide initiator (Fig. 11). Bleached soda pulp fibers
treated with 3% silane of APS or MPS (fiber content: 40 vol.%) were
incorporated into an unsaturated glycerophthalic polyester
OH
H
O
O Si (CH2)3 N
O
H
CH2
O
O Si (CH2)3 N
O
CH2
H
C
2 H2C
O
CH
CH
OH
epoxy resin
Fig. 10. Coupling reaction between APS-grafted natural fiber with epoxy resin.
Si
O
(CH2)3 O C C CH2
O
CH3
HC
+ m
UP resin
O C CH
CH2
CH
CH2
C O
CH2
O
CH3
O C CH CH
O
Si (CH2)3
O
Styrene
O C CH CH C O
CH2
O
peroxide
Fig. 11. Reaction of MPS-grafted fiber with unsaturated polyester resin in the presence of a peroxide initiator.
816
5. Outdoor performance
The moisture sorption of NFPCs measured according to standard
ASTM D-1037 [137] generally indicates very low moisture contents
(in a range of ca. 2%), although this depends upon the fiber contents. This has been attributed to the effect of the encapsulation
of fibers by polymers [138]; however, with the NFPCs in service
there often appears deleterious effects such as surface colour fading and erosion, warpage, mold growth, fungal decay, and strength
loss after a long-term exposure to an external environment
[21,139144]. These issues are mostly associated with the moisture sorption of the natural fibers. The moisture sorption of NFPCs
in service is slow and seldom reaches an equilibrium condition in a
moist environment. The core of the composites may have very low
moisture contents whilst the surface layers may be significantly
saturated with water [145]. However, even though it may take
time for the water to penetrate the core of such composites, the
water susceptibility of natural fibers remains a cause of concern,
which is particularly important if the fibers are exposed to moisture either through damage or cutting of the composite. Consequently, hydrophobation treatments of fibers thereby reducing
the moisture sorption are of importance for the NFPCs during environmental exposure in order to reduce potential damage associated with water.
Oil palm fibers modified with VTS in an alcoholwax mixture
(60:40) were soaked in water at different temperatures (30, 50,
70, and 90 C) to determine their water uptake behavior and the results showed that VTS-treatment reduced the water uptake of fibers at all temperatures used [146]. This makes the resulting
polymer composites drier under a moist environment thereby
reducing the risk of environmental damage such as deformation
and fungal decay [147]. Epoxy composites reinforced with sisal
which had been treated with APS or with jute fiber treated with
c-glycidoxypropyltrimethoxy silane (GPS) exhibited a reduced susceptibility of moisture on the flexural strength [19,58]. Coir or oil
palm fibers modified with MPS were incorporated into polyester
resin and the modifying effects on the resulting composites properties of water resistance and fungal decay were respectively
examined during one year weathering [148]. The mass loss due
to fungal decay reached over 15% for unmodified composites. In
comparison, MPS modified composites only lost 6% of the mass.
The modified composites after fungal test obtained a moisture content of 6%, less than the 12% observed with the unmodified composites. The low moisture content may be related to the reduced
mass loss due to fungal decay [147]. The tensile and flexural
strength of the modified composites were slightly reduced (up to
8%), which is distinctly less than over 30% for the unmodified
controls.
6. Summary
Most established silanes used for natural fiber/polymer composites are trialkoxysilanes bearing a non-reactive alkyl or reactive
organofunctionality. Silane is hydrolyzed forming reactive silanols
and is then adsorbed and condensed on the fiber surface (solgel
process) at a specific pH and temperature. The hydrogen bonds
formed between the adsorbed silanols and hydroxyl groups of natural fibers may be further converted into covalent bonds by heating the treated fibers at a high temperature, although such bonds
are susceptible to hydrolysis.
The interaction modes of the silane and matrix are dominated
by the organofunctionality of silane and the matrix characteristics.
Physical compatibility (such as molecular entanglement, or acid
base interactions) between silane-grafted fiber and thermoplastic
matrices only provides a limited improvement in the mechanical
properties of the resulting composites. To substantially improve
the interfacial adhesion, a chemical bonding between the organofunctionalities of silanes and the matrices is required. For the inert thermoplastic matrices, a free radical process is an effective
means to couple the vinylsilane treated fiber and matrices. In the
cases of thermoset matrices, the organofunctionalities of silanes
can react with the functional groups of thermoset matrices in the
presence of catalysts or radical initiators. Proper treatment of fibers with silane can increase the interfacial adhesion to the target
polymer matrices and improve the mechanical and outdoor performance of the resulting fiber/polymer composites.
Acknowledgement
The author Dr. Yanjun Xie would like to thank the German Academic Exchange Service (DAAD) for a research grant support.
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