Composites: Part A 41 (2010) 806–819

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Composites: Part A
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Review

Silane coupling agents used for natural fiber/polymer composites: A review

Yanjun Xie a,b,*, Callum A.S. Hill b, Zefang Xiao a, Holger Militz a, Carsten Mai a
a
Wood Biology and Wood Products, Burckhardt-Institute, Georg August University of Göttingen, Büsgenweg 4, D37077 Göttingen, Germany
b
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 a b s t r a c t

Article history: Natural fiber reinforced polymer composites (NFPCs) provide the customers with more alternatives in the
Received 9 November 2009 material market due to their unique advantages. Poor fiber–matrix interfacial adhesion may, however,
Received in revised form 4 March 2010 negatively affect the physical and mechanical properties of the resulting composites due to the surface
Accepted 4 March 2010
incompatibility between hydrophilic natural fibers and non-polar polymers (thermoplastics and thermo-
sets). 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
Keywords:
progress in using silane coupling agents for NFPCs, summarizes the effective silane structures from the
A. Silane coupling agents
A. Fibres
silane family, clarifies the interaction mechanisms between natural fibers and polymer matrices, and pre-
B. Fiber/matrix bond sents the effects of silane treatments on the mechanical and outdoor performance of the resulting
B. Environmental degradation composites.
Crown Copyright Ó 2010 Published by Elsevier Ltd. All rights reserved.

1. Introduction and background
Natural fiber reinforced polymer composites (NFPCs), as an
important branch in the field of composite materials, have been
studied for decades [1–11]. Natural fibers have different origins
such as wood, pulp, cotton, bark, nut shells, bagasse, corncobs,
bamboo, cereal straw, and vegetable (e.g., flax, jute, hemp, sisal,
and ramie) [10–13]. These fibers are mainly made of cellulose,
hemicelluloses, lignin and pectins, with a small quantity of
extractives. The fiber constituents vary depending on their origi-
Abbreviations: ABI, acid–base interaction; APS, c-aminopropyl triethoxy silane;
ASE, anti-swelling efficiency; BDMA, benzyl dimethylamine; BPO, benzoyl perox-
ide; CTMP, chemithermomechanical pulp; DCUP, dicumyl peroxide; DCS, dichlo-
rodiethylsilane; DGEBA, diglycidyl ethers of bisphenol A; DMA, dynamic
mechanical analysis; DMVS, dichloro methyl vinyl silane; DSC, differential scanning
calorimetry; EMC, equilibrium moisture content; FTIR, Fourier transform infrared
spectroscopy; GPS, c-glycidoxypropyltrimethoxy silane; HDS, hexadecyltrimethoxy
silane; IPN, interpenetrating polymer network; ISS, interfacial shear strength; LDPE,
low density polyethylene; MAPP, maleated polypropylene; MEKP, methyl ethyl
ketone peroxide; MMS, methacryloxymethyltrimethoxy silane; MPS, c-methacryl-
oxypropyl trimethoxy silane; MRPS, c-mercaptopropyltrimethoxy silane; NFPCs,
natural fiber reinforced polymer composites; PALF, pineapple leaf fiber; PAPS, c-
phenyl-aminopropyltrimethoxy silane; PE, polyethylene; PP, polypropylene; PS,
polystyrene; PVC, polyvinyl chloride; SEC, size exclusion chromatography; TAS, c-
diethylenetriaminopropyl trimethoxy silane; TGA, thermogravimetric analysis; UP,
unsaturated polyester; VSPP, vinyltrimethoxysilane grafted polypropylene; VTS,
vinyltrimethoxy silane; XPS, X-ray photoelectron spectroscopy.
* Corresponding author at: Centre for Timber Engineering, School of Engineering
and the Built Environment, Edinburgh Napier University, 10 Colinton Road, EH10
5DT Edinburgh, United Kingdom. Tel.: +44 131 4552494; fax: +44 131 4552239.
E-mail address: y.xie@napier.ac.uk (Y. Xie).
nation. Compared with conventional inorganic fillers such as glass
fiber and carbon fibers, natural fibers provide many advantages:
(1) abundance and therefore low cost, (2) biodegradability, (3)
flexibility during processing and less resulting machine wear,
(4) minimal health hazards, (5) low density, (6) desirable fiber as-
pect ratio, and (7) relatively high tensile and flexural modulus.
Incorporating the tough and light-weight natural fibers into poly-
mer (thermoplastic and thermoset) matrices produces composites
with a high specific stiffness and strength [14]. The renewable
and biodegradable characteristics of natural fibers facilitate their
ultimate disposal by composting or incineration, options not pos-
sible with most industrial fibers. The fibers also contain seques-
tered atmospheric carbon dioxide in their structure and are
invariably of lower embodied energy compared to industrially
produced glass fibers.
Although natural fibers can offer the resulting composites many
advantages, the usually polar fibers have inherently low compati-
bility with non-polar polymer matrices, especially hydrocarbon
matrices such as polypropylene (PP) and polyethylene (PE)
[15,16]. The incompatibility may cause problems in the composite
processing and material properties. Hydrogen bonds may form be-
tween the hydrophilic fibers, and thus the fibers tend to agglomer-
ate into bundles and unevenly distribute throughout the non-polar
polymer matrix during compounding processing [17,18]. There is
also insufficient wetting of fibers by the non-polar polymer matri-
ces, resulting in weak interfacial adhesion. As a result, the stress
transfer efficiency from the matrix to the reinforcing fibers is re-
duced. The incompatibility may not be an issue when using polar
polymers such as unsaturated polyester (UP) and epoxy resin as

1359-835X/$ - see front matter Crown Copyright Ó 2010 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2010.03.005
 Y. Xie et al. / Composites: Part A 41 (2010) 806–819
matrices; however, the resulting composites, similar to the com-
posites with non-polar matrices, will be susceptible to moisture
deterioration and fungal damage during outdoor service. The mois-
ture 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 com-
posite 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 crit-
ical to obtain the improved physical and mechanical properties of
the resulting composites. Physical treatments (e.g. electronic dis-
charge in the different media such as plasma and corona technol-
ogies [22–25]) 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 fi-
bers. 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 im-
pact 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 sur-
face 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) [18,31–33]. The anhy-
dride groups of the copolymers may react with the surface hydro-
xyl 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 be-
tween the isocyanate functionality and the hydroxyl group of nat-
ural 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]. Si-
lanes 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 compos-
ites are discussed and the interaction mechanisms between phases
clarified.
807
2. Silane structures and hydrolysis processes
2.1. Silane structures
To effectively couple the natural fibers and polymer matrices,
the silane molecule should have bifunctional groups which may
respectively react with the two phases thereby forming a bridge
in between them. Silane coupling agents have a generic chemical
structure R(4n)ASiA(R0 X)n (n = 1,2) where R is alkoxy, X repre-
sents an organofunctionality, and R0 is an alkyl bridge (or alkyl
spacer) connecting the silicon atom and the organofunctionality.
In the past decades, various silane structures have been tested
for coupling of inorganic reinforcements such as glass fiber and
organic polymer matrices. The structures used to couple the nat-
ural fibers and polymer matrices are relatively limited. Most of
the established silanes used for NFPCs are trialkoxysilanes. The
organofunctionality of the silane interacts with the polymer
matrices with their interaction modes depending on the function-
ality’s reactivity or compatibility towards the polymer. A non-
reactive alkyl group of the silane may increase the compatibility
with non-polar matrix due to their similar polarities; however,
the reactive organofunctionality may covalently bond with as
well as being physically compatible with the polymer matrices.
These organofunctionalities of silanes are typically amino, mer-
capto, glycidoxy, vinyl, or methacryloxy groups. The most re-
ported silanes and their applied target polymer matrices are
listed in Table 1.
With regard to these silanes shown in Table 1, aminosilanes,
especially c-aminopropyltriethoxysilane (APS), are most exten-
sively reported in the literature as coupling agents between natural
fibers and thermoplastics or thermosets. Vinyl- and acryl-silanes
are coupling agents that are able to establish covalent bonds with
polymeric matrices in the presence of peroxide initiators. Methac-
rylate–functional silanes can display high levels of reactivity with
unsaturated polyester matrices [44], whilst azidosilanes can effi-
ciently couple inorganic fillers with thermoplastic matrices
[62,63]; however, there have been few reports of their use in nat-
ural fiber reinforced thermoplastic composites. The application and
effects of these typical silanes on the NFPC’s properties will be pre-
sented below.
2.2. Hydrolysis processes of silanes
The alkoxysilanes have been demonstrated to be able to directly
react with ASiAOH groups of silica thereby forming ASiAOASiA
bonds [e.g. 43,67,68] without any requirement of prehydrolysis.
However, silanes do not undergo the same reaction with the hy-
droxyl groups of cellulosic fibers even at high temperature [69].
This has been attributed to lower acidity of cellulosic hydroxyl
groups compared with silanol [69]. In addition, cellulose is gener-
ally unreactive to many chemicals and the OH groups of the micro-
fibrils have very low accessibility. Based on the fact, an optional
strategy is to activate the alkoxysilane by hydrolyzing the alkoxy
groups off thereby forming the more reactive silanol groups. As a
result, the silanol may react with the hydroxyl groups of fibers or
condense themselves on the surfaces of fibers and/or in the cell
walls forming macromolecular network. Although the formed
ASiAOACA bonds are eventually not stable towards hydrolysis,
blocking the hydroxyl groups (reversible to hydrolysis) and the for-
mation of macromolecular network (permanent) under heating
condition facilitate an enhancement of interfacial adhesion of trea-
ted fibers and polymer matrices and of the properties of the result-
ing composites. To hydrolyze the alkoxy groups off, participation of
water is essential. Even though the natural fibers under room
condition contain bound water which may act to hydrolyze the
808 Y. Xie et al. / Composites: Part A 41 (2010) 806–819

Table 1
Silanes used for the natural fiber/polymer composites: chemical structures, organofunctionalities and target polymer matrices.

Structure Functionality Abbreviation Target matrix References

(RO)3SiA(CH2)3ANH2a Amino APS Epoxy [19,44–47]
Polyethylene
Butyl rubber
Polyacrylate
PVC
(RO)3SiACH@CH2 Vinyl VTS Polyethylene [44,48–52]
Polypropylene
Polyacrylate
(RO)3SiA(CH2)3AOOC(CH3)C@CH2 Methacryl MPS Polyethylene [20,44,53,54]
Polyester
(RO)3SiA(CH2)3ASH Mercapto MRPS Natural rubber [53,55–57]
PVC
(RO)3SiA(CH2)3AOACH2CHCH2O Glycidoxy GPS Epoxy [19,45,58,59]
Butyl rubber
Polysulfide
R2ASiACl2 Chlorine DCS Polyethylene [47,60]
PVC
VTS grafted plastics Vinyl VSPP Polypropylene [52,61]
VSPE Polyethylene
(RO)3ASiAR00 AN3b Azide ATS Polypropylene [62–64]
Polyethylene
Polystyrene
(RO)3SiA(CH2)15CH3 Alkyl HDS Polyethylene [53,65,66]
Natural rubber
a
R = Amethyl or ethyl.
b
R00 = AC6H4ASO2A.

silanes; however, additional water is required to achieve a com- 2.2.2. Effect of hydrolytic conditions on the hydrolysis of silane
plete hydrolysis of silanes [70–72]. In the presence of water, the silane will undergo a hydrolysis
process. The alkoxysilanes are hydrolyzed thereby forming alkoxy-
silanol mono- and di-, and then eventually silane tri-ols. To fully
2.2.1. Effect of silane structures on the hydrolysis hydrolyze one mole of trialkoxysilane, at least three moles of water
Alkoxy groups associated with silane coupling agents prior to is needed. Once the silanol groups form in the solution, the con-
utilization can be hydrolyzed off thereby liberating the corre- densation between silanol groups also starts, therefore generating
sponding alcohols in the presence of water and generating reactive a siloxane (ASiAOASiA) polymer network in the solution. Thus,
silanol groups. The alkoxy groups are usually ethoxy or methoxy. the sol evolves towards the formation of a gel-like diphasic system
Under the same hydrolytic conditions the methoxy groups of tri- containing both a liquid phase and solid phase whose morpholo-
methoxysilane hydrolyzes more rapidly than the ethoxy groups gies range from discrete particles to continuous polymer networks.
of triethoxysilane [73]. The hydrolysis of trimethoxysilane produc- The competition of alkoxy hydrolysis and silanol condensation are
ing methanol may be more environmentally problematic than the
triethoxysilane releasing ethanol because methanol is more toxic
than ethanol. The number of alkoxy groups will determine the
amount of water used to fully hydrolyze them and influence the OR
adhesion between silanes and filler. Di- and tri-alkoxy silanes pro-
duce stronger adhesion strength than mono-alkoxy silanes since (a) RO Si CH2 X
they form more binding sites after they are hydrolyzed [74]. If it
is desired to deliver an alkoxy functional silane to the interior of OR
the fiber this can be accomplished by dissolving the silane in the
appropriate alcohol (e.g. ethanol for an ethoxy silane). Hydrolysis OR
can then be achieved by subsequent water treatment.
The length of the alkyl spacer between the silane organofunc- (b) RO Si (CH2 )3 X
tionality and the silicon atom also influences the hydrolysis rate
of the silane (Fig. 1a and b). For example, a-methacryloxymethyl- OR
trimethoxy silane (MMS, a-silane) hydrolyzes 20 times faster than
c-methacryloxypropyltrimethoxy silane (MPS, c-silane) in an ace- R1(O) CH2
tone/water mixture at pH 4 [75]. This has been attributed to the so-
called ‘‘a-effect” of silanes. The shorter alkyl spacer causes higher (c) R1O Si N R2
reactivity of alkoxy groups due to the stronger electron interaction
between the functionality (X) and the silicon atom. Such effects R1(O) R2
may be explained using a-aminoalkylsilanes as an example, where
Fig. 1. Different length of the bridge connecting the silicon atom and functional-
back-bonding of the nitrogen’s free electron pair to the silicon ities: a-silane having a methylene spacer (a), c-silane bearing a propylene spacer
atom weakens the SiAO bonds thereby causing a higher reactivity (b), and the schematic diagram of the ‘‘a-effect” in the aminomethylene silane (c)
of alkoxy group (Fig. 1c). [75].
 Y. Xie et al. / Composites: Part A 41 (2010) 806–819 809

affected by the hydrolysis condition used such as the solvent, tem- R' OR
perature, pH, concentration of silanes [76–78]. Under optimum RO OR
conditions hydrolysis may be accelerated, but condensation of sil-
(a) Si Si
anols is inhibited to maintain a stable intermediary structures such RO O R'
as silanol monomer or dimers [76,79,80]. T1structure
The dynamics of the hydrolysis and ensuing condensation of dimer or chain end
several trimethoxysilanes bearing different chain length of alkyl
functionalities (methyl, ethyl, propyl, or butyl) have been investi-
gated in water–acetone mixtures by quantifying the produced R' OR R'
methanol using internal reflection Fourier transform infrared spec- RO R' OR
(b) Si Si Si
troscopy (FTIR) combined with statistical regression. The results
RO O O OR
show that the relative rates of the consecutive hydrolysis reactions
and the rate of condensation to form siloxane bonds depend on the T2 structure
silane organofunctionalities, and this FTIR technique permits the
linear link
tailoring of the composition of the alkoxysilane compounds in
solution to obtain the desired rate and degree of hydrolysis of alk-
oxy groups, and the extent of siloxane bond formation [82]. The R' R' R'
hydrolysis rates of APS, c-diethylenetriaminopropyl trimethoxy si-
RO OR
Si Si Si
lane (TAS) and MPS were established using 1H NMR by measuring (c) RO O O OR
the evolution of liberated free alcohol, and it showed that the rate O
increased in the order MPS < APS < TAS. The formation of the sila-
nol groups was followed by their condensation to generate oligo- Si
meric structures. Whereas APS and MPS only gave soluble RO OR
products, colloidal particles by contrast precipitated in the med- R'
ium when the TAS was hydrolyzed [83,84]. At alkaline pH, the alk-
T3 structure
oxy groups of APS were hydrolyzed almost immediately in water
and the resulting aminosilanols formed a cyclic structure with an three dimensional
internal hydrogen-bonded ring (Fig. 2). Bonding of the silanol
R' = functional group; R = alkyl group
hydrogen makes the silanol stable against condensation in the con-
centrated aqueous solutions. As a result, there was no insoluble gel Fig. 3. Schematic presentation of Ti silane structures [72].
in an alkaline aqueous solution of the aminoalkylsilanes after sev-
eral months of storage [43]. In the pH range of 3–6, aminosilanol
groups in the solution were relatively more stable, existing as zwit-
terionic structures [43]. In contrast, MPS hydrolyzes much slower 3. Interaction mechanisms between silanes and natural fibers
and requires the use of an amine as catalyst in the water/solvent
solution [83]. 3.1. Fiber surface coating and cell wall modification
Generally, under acid-catalyzed conditions, the hydrolysis rate
of silanes forming silanol groups is greater than the condensation In the present literature, there are several different means re-
rate of the ensuing silanols forming siloxane bonds [72,79]. These ported to apply silanes to natural fibers. These can be divided into
competing reactions of hydrolysis and condensation in an etha- fiber surface treatment and cell wall modification. Spraying is a rel-
nol/water (80/20, w/w) solution at different pH values were ascer- atively easy way to treat the fiber surface with a silane solution.
tained in situ using 1H, 13C, and 29Si NMR spectroscopy [72]. After The silanes are dissolved into certain organic solvents or solvent/
hydrolysis of the silane, the ensuing silanol groups gradually self- water mixtures and the prepared solution is directly sprayed onto
condensed into the structures of dimer (T1) (Fig. 3a), linear siloxane the fibers. If the solution is water-free, the sprayed silanes can be
(T2) (Fig. 3b), and ultimately rigidly three-dimensional polysilox- partly hydrolyzed via the reaction with water from fibers and air.
ane cage structures (T3) (Fig. 3c). In an acidic solution, the hydroly- Due to the fast evaporation of solvent in air, the nano-pores of cell
sis rate of MPS was accelerated and the self-condensation rate was walls cannot be opened up and thereby the silane molecules will
reduced compared to those in the alkaline solution. The entities hardly penetrate into fiber cell walls, because it will take many
with T3 units appeared after more than 1 month under acidic con- hours for the chemical to diffuse into dense fiber cell walls from
ditions; however, they appeared after only 6 h in the alkaline solu- the solution [29]. As a result, spraying only results in a surface
tion. The formation of a T3 structure in the treating solution must coating with silanes and the inside of cell walls is left untreated.
be inhibited since this may reduce the number of silanol groups In one method, silane solution and initiator were directly
adsorbed to fibers. The silanol condensation will also make the cell pumped into an extruder during an extrusion process of natural fi-
wall penetration by silane impossible due to the increased molec- bers and thermoplastic matrices. The extruded composites were
ular size. subsequently exposed to an environment with high humidity and
temperature (ca. 100% relative humidity and 90 °C) in order to
complete the hydrolysis and condensation processes of the silane
[50]. This technique is simple at the initial stage but it will take a
O CH2CH2 long time at the hydrolysis and condensation stage. In addition,
the silanes added will not only distribute on the interface of fiber
Si CH2 and matrices, but some also in the matrices. This causes inefficient
utilization of the silanes added. This process technique is also to be
O OH NH2 seen as a surface treatment.
In another approach, thermoplastic matrices were grafted with
Fig. 2. A proposed cyclic hydrogen-bonded amine structure in the hydrolytic APS silanes and the grafted pre-polymers were used as a new coupling
solution [81]. agent directly blending with natural fibers and thermoplastic
810 Y. Xie et al. / Composites: Part A 41 (2010) 806–819
matrices [52]. Through this method of application, the alkoxysil-
anes 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 re-
ported [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 pro-
mote the performance improvement of the ensuing composites.
Compared to the surface treatment such as spraying, the impreg-
nation 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, form-
ing 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 re-
sults in the formation of a rigid polysiloxane layer on the fiber sur-
face. 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 hydro-
lysis conditions such as pH of solution have to be adjusted to slow
down the condensation thereby allowing the reactive silanol ac-
cess to hydroxyl sites in the fiber cell walls. Both, APS and TAS, dis-
played 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-amino-
propyltrimethoxy silane (PAPS) shows the lowest adsorption affin-
ity 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 difficul-
ties 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 sol-
vent evaporation as evidenced by 29Si NMR study [72]. Unlike the
SiAOAC bonds, the ASiAOASiA bonds formed are very stable to-
wards 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 [88–90], 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 re-
move 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 evi-
dence 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
[87,92–94]. Heating also promotes the condensation of free silanol
groups resultantly forming the solid polysiloxane layers on the fi-
ber 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 hy-
droxyl groups of fibers. These interactions in the aminosilane-trea-
ted 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 envi-
ronment. Hydrolysis of ASiAOACA bonds will produce the free sil-
anol 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 fi-
bers 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 sila-
nols is controllable by adjusting the pH of the hydrolysis sys-
tem. 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 olig-
omers are physically adsorbed to hydroxyl groups of natural
fibers by hydrogen bonds on the fiber surfaces (surface coat-
ing) and/or in the cell walls (cell wall bulking), which
depends on the molecular size of silanol monomers/oligo-
mers 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 fi-
bers 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
 Y. Xie et al. / Composites: Part A 41 (2010) 806–819 811

OR OH
H or OH
(a) Hydrolysis: R' Si OR + 3 H2O R' Si OH + 3 ROH
OR OH

OH OH OH OH
(b) Self-condensation: R' Si OH + HO Si R' R' Si O Si R' + H2O
OH OH OH OH

O O

R' Si O Si R'
O O + x H2O
R' Si O Si R'

O O

OH
OH
O HO Si R'
O HO Si R' H
H OH
(c) Adsorption: OH
+
OH OH OH OH
O HO Si O Si R' O HO Si O Si R'
H H
R' OH R' OH

OH

HO Si R' O
O
H
OH Δ O Si R'
(d) Chemically grafting: O O + x H2O
OH OH
O Si O Si R'
O HO Si O Si R'
H R' O
R' OH

Fig. 4. Interaction of silane with natural fibers by hydrolysis process.

15 h Soxhlet extraction with ethanol [87]. Donath et al. [97] deter-
mined the anti-leaching ability of wood treated with the oligomers
of methyl- and propyl-triethoxysilane and a multifunctional aque-
ous siloxane HS 2909 (with the functionalities of alkyl and amino
groups). Both silane oligomers, especially the latter, cannot be lea-
ched out of pine wood after treatment. Both silanes MPS and vinyl-
trimethoxy 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 rea-
son. 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 hydro-
phobic reinforcement for non-polar polymer matrices. A surface
coating only decreases the water sorption rate and does not sub-
stantially reduce the amount of water to be absorbed because
the cell walls are not filled with polymeric silane. In contrast, a bul-
king treatment may reduce the cell wall nano-pore size and deac-
tivate or mask the hydroxyl functionalities thereby decreasing
water sorption [86]. Hydrophobation treatments can weaken the
hydrogen bonds between natural fibers and the agglomeration of
fibers is thus reduced during compounding with non-polar poly-
mer matrices.
Treatments of a commercial microcrystalline cellulose fiber
with a silane solution of APS, MPS, hexadecyltrimethoxy silane
(HDS), or c-mercaptopropyltrimethoxy silane (MRPS) in an etha-
nol/water (80/20 v/v) mixture caused a significant increase in the
water contact angle of treated fibers from an original value of
20° (untreated control) up to 110° determined by a dynamic con-
tact angle test [65,66]. The polar component of the fiber surface en-
ergy is reduced and the non-polar component increases due to the
treatments with alkylsilane such as propyltrimethoxysilane and
HDS [59,66,98–100]. Optical microscopy showed that treatment
of flax fibers with VTS reduces the heterogeneous nucleation of
PP crystals on flax fibers and the treated fiber surfaces were
smoother than the untreated fibers [99]. Treatment of sisal fibers
with 1% MPS in benzene has been reported to reduce the equilib-
rium moisture content (EMC) of fibers from 12.8% to 1.7% and
the water absorption from 123.8% to 64.4% [20]. However, since
benzene does not swell the fiber cell wall the penetration of MPS
in the cell walls may consequently be limited and the reduction
in moisture/water sorption may mainly be due to the hydrophobic
effect of the surface coating. Compared to the silanes bearing non-
polar alkyl groups, treatments with APS or PAPS which bear polar
812 Y. Xie et al. / Composites: Part A 41 (2010) 806–819

amino groups only resulted in a minor reduction of the moisture
content of jute fibers [59]. This may be due to the highly hydro-
philic characteristics of the amino end group.
3.3.3. Effect on the thermostabilization
Silane treatment of fibers could affect the thermal stability of
natural fibers. During the processing of composites, the natural fi-
bers are subject to intense heat in the compounding machine or
extruder. Therefore, a positive effect on the thermal properties is
desired. The thermal stability of silane-treated flax fibers was stud-
ied using thermogravimetric analysis (TGA) at a temperature range
of 30–800 °C in a helium atmosphere [101]. The fibers were treated
by immersing them into the VTS aqueous solution for 1 h to obtain
a weight percent gain of 2.5%. The treated fibers exhibited an im-
proved thermal stability of hemicellulose and pectin. Kinetic anal-
ysis of the degradation process using Kissinger equation showed an
activation energy which proved to be 22% higher for VTS-treated
fibers than the untreated controls.
3.3.4. Effect on the fiber strength
The treating system should not contain any fiber-damaging ele-
ment such as an acidic catalyst (for hydrolysis) or include high
temperature. The acidic conditions (ca. pH 4.0), in some cases, for
the acid-catalyzed hydrolysis of silanes were moderate and the
pH was close to that of many natural fibers. As a result, silane treat-
ment caused little effect on the fiber tensile strength [47,59,102].
Varma et al. [103] reported, however, a 35% and 19% tenacity loss
of coir fibers after refluxing in a benzene solution of 0.5% dichloro
methyl vinyl silane (DMVS) or of 2% MPS, respectively (Table 2);
however, these tenacity losses are mostly thought to have been
caused by the benzene (24%), rather than the silane itself (Table 2).
4. Interaction with polymer matrices
4.1. Coupling with thermoplastic matrices
4.1.1. Inter-phase compatibility
The interaction mode between the silane-treated fiber and the
polymer matrix is a crucial factor for the mechanical properties
of the resulting NFPCs. Physical blending of the silane-treated fi-
bers and the thermoplastic matrices enhances their mutual adher-
ence via inter-molecular entanglement, or acid–base interactions
(ABI) [43]. The interfacial shear strength (ISS) between jute fibers
and PP, determined by a microdroplet micromechanical test, was
improved by treating jute fibers with a 0.5% APS aqueous solution
[104]. Treatment of aspen chemithermomechanical pulp (CTMP,
mesh 60 lm) with a 4 wt.% ethanol solution of silane VTS or MPS
did not substantially enhance the tensile properties of the resulting
polyethylene composites compared to the untreated composites
[105]. The composites made from the fibers treated with silane,
such as HDS or dichlorodiethylsilane (DCS) merely bearing a non-
reactive aliphatic chain, displayed only a moderate improvement
in the mechanical properties of the composite [47,53,106,107].
Table 2
Effect of silane treatment on mechanical properties of coir fibers [103].
Treatment Time Tenacity (g/ Elongation at Initial modulus (g/
(h) denier) break (%) denier)
Untreated – 2.26 28.80 38.30
2% MPS 1.00 1.82 23.52 36.09
0.5% 0.50 1.47 22.44 30.13
DMVS
0.5% 0.25 1.80 26.12 34.20
DMVS
Benzene 1.00 1.71 23.72 35.94
The limited coupling effects on the mechanical strength of the
NFPCs due to the absence of covalent bonds between the silane
functionality and thermoplastic matrices are exemplified in Ta-
ble 3. The marginal improvements in the mechanical properties
of the composites were mainly attributed to the increased compat-
ibility resulting from the uniform dispersion of silane-treated fi-
bers into the thermoplastic matrices [47]. The thermoplastic
molecular chains may also diffuse into the rigid polysiloxane struc-
tures on the fiber surface forming an entangled ‘‘interpenetrating
polymer network (IPN)” [43,94,108,109].
In the case of aminosilanes, the amino groups cannot react with
the hydrocarbon backbone of PP or PE, but the natural fibers and
thermoplastic composites coupled with APS was reported to pro-
vide somewhat better mechanical properties than the uncoupled
ones [47,110]. Such improvements have been proposed to be due
to the strong affinity of the amino group towards the hydroxyl
groups of fibers and to the formation of a cage-like IPN composed
of the polysiloxane structures [43,44]. The IPN network can entrap
the thermoplastic molecules thereby anchoring the thermoplastic
matrices to the treated fiber surface. In addition, acid–base interac-
tions (ABI) may also play a role in determining the interfacial adhe-
sion of composites composed of the aminosilane-treated fibers and
specific thermoplastic matrices bearing acidic or basic characteris-
tics, e.g. polystyrene (PS) and polyvinyl chloride (PVC) [47,111].
The calculation according to electron donor and acceptor numbers
of organic molecules indicates that the cellulosic fibers treated
with aminosilane have both the acidic (KA) and basic (KB) charac-
teristics, and the basicity is more prominent than the acidity
(KA = 0.33, KB = 0.52) [111]. This ‘bipolar’ characteristic enhances
the interactions of aminosilane-treated fibers with the ‘bipolar’
polystyrene (KA = 0.28, KB = 0.46) [111] or PVC (KA = 1.43,
KB = 0.65) [47] since the acidic sites from the aminosilane-treated
fibers can interact with the basic sites of thermoplastic matrices
and vice versa. Reinforced polystyrene composites with the cellu-
lose fibers treated with different structures of silanes show a linear
increase in the maximum interfacial shear stress (ISS) with the
acid–base interaction value (Ia–b) between the treated cellulose fi-
bers and polystyrene matrix [111]. For the studied silanes with a
functionality of phenyl (C6H5), phenylamino ((CH2)3NHC6H5), ami-
no ((CH2)3NH2) or octadecyl ((CH2)17CH3), the aminosilane-treated
fibers display a stronger acid–base interaction with polystyrene
than the other silanes, and hence obtain stronger interfacial adhe-
sion [111]. Similar to a polystyrene matrix, interaction of the acidic
PVC and basic APS also showed acid–base characteristics (Fig. 5)
[47,57]. Compared to the untreated fiber/PVC composites, the
PVC composites reinforced with the APS-modified fibers displayed
an increase up to 36% in the tensile strength due to the high Ia–b va-
lue between treated fiber and PVC; however, treatment with DCS
did not change the Ia–b of two components of the composite and
thus the tensile strength of resulting PVC composites did not
change [47].
4.1.2. Radical grafting
As presented above, physically blending of the silane-modified
natural fibers and thermoplastic matrices only produces a limited
improvement in the mechanical properties of the resulting com-
posites (Table 3). To substantially improve the mechanical prop-
erties of natural fiber and thermoplastic composites, the
formation of a covalent bond between the silane and non-polar
thermoplastic matrix seems to be necessary [113]. It should, how-
ever, be noted that a strong coupling between a reinforcing fiber
and the matrix can result in a brittle composite especially with
thermoset matrices [114]. However, most thermoplastic resins
do not bear any reactive functionality. As a result, the silane-trea-
ted natural fibers cannot react with the target thermoplastic to
form any covalent bond during the compounding process, either
 Y. Xie et al. / Composites: Part A 41 (2010) 806–819 813

Table 3
Improvement (%) in tensile properties of natural fiber/thermoplastic composites coupled with different functionalities of silanes in the absence of initiators.

Silane (%) Fiber treatment with silane Fiber (%) Polymer Improvement (%) References
Tensile Tensile Elongation at break Energy at yield
strength modulus
VTS (4) Immersion in ethanol/water CTMP (40) LDPE 27 65 107 16 [105]
MPS (4) Immersion in ethanol/water CTMP (40) LDPE 9 74 245 25 [105]
APS (4) Immersion in p-xylene CTMP (30) PS 6 25 18 19 [44]
MPS (2) Spray with aqueous solution Wheat straw fiber PP 2 10 6 – [112]
HDS (3) Immersion in ethanol/water Cellulosic fibers LDPE 6 7 – – [53]
MRPS (3) Immersion in ethanol/water Cellulosic fibers LDPE 12 6 – – [53]
APS (0.01) Immersion in acetone Pine TMP (10)a PE 1 – – – [47]
DCS (0.1) Dry blending Newsprint fiber (45) PVC 5 15 30 – [47]
a
TMP: thermomechanical pulp.

Cl
O Δ O
O Si (CH2) 3 NH2 + Cl O Si (CH2)3 NH
O O

APS grafted fiber PVC

Fig. 5. Acid–base reaction between APS-modified fibers and PVC matrix [47].

in the mixers or in the extruders. An effective means to covalently
bond the silane to a thermoplastic matrix is by free radical graft-
ing [113,115] or by plasma discharge [116]. The mostly reported
applications are to graft VTS or MPS onto a thermoplastic matrix
in the presence of peroxide initiators such as benzoyl peroxide
(BPO) or dicumyl peroxide (DCUP) [e.g. 44,49]. At an elevated
temperature the peroxide first decomposes, generating oxy radi-
cals. The oxy radicals not only have the potential to abstract
hydrogen from the backbone of thermoplastic molecules or natu-
ral fibers, but can also add to vinyl double bonds of vinylsilane,
producing vinyl radicals. The vinyl free electron may either com-
bine with each other (homo-polymerization) or attack the other
molecules in a similar fashion to propagate the free radical reac-
tion. A previous study showed, however, that VTS did not homo-
polymerize 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 cou-
pling 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 vinylsi-
lane treated fibers and thermoplastic matrices.

CH 2 CH 2
R-O-O-R
CH 2 HC .
Δ
CH 2 CH 2

PE chain PE radical

OR

OC 2 H 5 CH 2 OC 2 H 5
R-O-O-R
H2C CH Si OC 2 H 5 . CH Si OC 2 H 5
Δ
OC 2 H 5 OC 2 H 5

OR OR

CH 2 CH 2 OC 2 H 5 CH 2 CH 2 OC 2 H 5
Grafting
HC . + . CH Si OC 2 H 5 HC CH Si OC 2 H 5

CH 2 OC 2 H 5 CH 2 OC 2 H 5

Fig. 6. Radical grafting of vinylsilane onto polyethylene matrix.

814 Y. Xie et al. / Composites: Part A 41 (2010) 806–819

Table 4
Mechanical properties of natural fiber/thermoplastic composites coupled with the representative vinylsilanes in the presence of peroxide initiator.

Components of composite Improvement in mechanical properties (%) References

Fiber (%) Polymer Silane (%) Initiator (%)
Henequen (20) HDPE VTS (1) DCUP (0.5) ca. 30% in tensile strength, 50% in Iosipescu shear strength [91,94,124]
CTMP of aspen (30) LDPE MPS (4) DCUP (unclear) 38% in tensile strength, 13% in tensile modulus [51]
Wood flour (40) HDPE VTS (2) DCUP (0.17) 87% in flexural strength, 18.8% in flexural modulus, [50,121,122]
more than 100% in impact strength
Flax (30) PP MPS (3) DCUP (0.3) More than 60% in tensile strength [106]
CTMP of aspen (30) LDPE VTS (4) DCUP (unclear) 66% in tensile strength, 44% in tensile modulus [51]
CTMP of spruce and balsam fir (20) PVC MRPS (2) BPO (0.8) 98% in tensile strength [57]

4.1.2.1. Copolymer as new coupling agent. Grafting of VTS alone onto

low density polyethylene (LDPE) with different concentrations of OR O
VTS (0–27.33 part per hundred (phr)) and BPO (0–1.25 phr) has re-
vealed that the VTS grafted polyethylene produced a maximum RO Si R' S N3
tensile strength at the concentrations of 5.0 phr VTS and 0.25 phr
BPO [118]. The grafting efficacy of VTS and maleic anhydride onto OR O
PP in the presence of DCUP were studied and the results demon-
strated that VTS has a higher reactivity towards PP than maleic Fig. 7. A general chemical formula of azidosilane. Representatively, R0 = aryl-
containing group.
anhydride [61,119]. When the copolymers of VTS grafted polypro-
pylene (VSPP) and MAPP were respectively used as a new coupling
agent to couple wood flour and PP matrix, VSPP coupled compos- tional azido group can react with thermoplastic matrices forming
ites were 47% stronger in tensile strength and 35% lower in water covalent bonds (Fig. 8). Upon heating, the azide may decompose
uptake than the composites coupled with the copolymer MAPP forming a highly reactive intermediate nitrene and simultaneously
[52]. The study from Arbelaiz et al. [120] also reveals a superiority releasing a nitrogen molecule. The nitrene can react with any of the
of VSPP to MAPP used as the coupling agents. MAPP has been CAH bonds in the thermoplastic polymer by inserting itself into
extensively studied and is well known to be an excellent coupling the carbon–hydrogen single bond or by adding to a carbon–carbon
agent in the bonding of natural fibers and thermoplastic matrices. double bond or aromatic system [126]. The required temperature
This provides a means to further improve the interfacial properties for the covalent reaction is below 200 °C (in the temperature range
of the NFPCs by using the VSPP copolymer. of thermal process of NFPCs) and the reaction does not need any
peroxide initiator. Accordingly, azidosilanes would also be of great
4.1.2.2. Grafting reaction between the silane-treated fiber and matri- interest to couple natural fibers and polymer matrices. However,
ces. A study of the melt rheological behavior showed that treat- the application of azidosilanes on the NFPCs is little reported.
ment of pineapple fibers with VTS (4.0 wt.% of fiber) and
peroxide DCUP (2.0 wt.% of fiber) caused an increase in the melt
4.2. Coupling with thermosetting resins
viscosity of the resulting LDPE composites. This was attributed to
the increased fiber–matrix interfacial interaction due to a grafting
In contrast with thermoplastic resins, the thermosetting resins
reaction. Treatment of pineapple fibers with the peroxides DCUP
(thermosets) are usually liquids prior to curing, bear reactive
(0.5 wt.% of LDPE) or BOP (1.0 wt.% of LDPE) alone also increased
organofunctionalities and thereby are able to form three-dimen-
the melt viscosity of resulting LDPE composites due to the free rad-
sional networks after a curing reaction. Compared to thermoplas-
ical grafting reaction between fibers and LDPE at a high tempera-
tics, thermoset resins are more reactive towards the
ture (125–145 °C) [49]. The grafting reaction of VTS-treated wood
organofunctionalities of silanes. Unlike the extrusion process of
flour with PE in the presence of DCUP initiator caused a significant
natural fiber/thermoplastic composites where there is a shear fail-
increase in the flexural strength (up to 87%) and impact strength
ure of long fibers, the long natural fibers can be easily incorporated
(more than 100%) of the resulting extruded composites
into the thermosetting resins without any damage from the pro-
[50,121,122]. The reported effects of grafting vinylsilanes with dif-
ferent thermoplastic matrices on the mechanical properties of
resulting NFPCs are exemplified in Table 4. OR OR
Grafting effects of vinylsilane on the mechanical properties of
OH + RO Si R" N3 O Si R" N3
the resulting NFPCs depended on the types of thermoplastic matri-
OR OR
ces [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 OR OR
of fibers with the same treatment into a polystyrene matrix did not O Si R" N3 O Si R" N: + N2
substantially improve the mechanical properties of the ensuing Δ
OR OR
composites compared to the untreated fiber reinforced composites
[44]. It may be concluded that the proper match of silane organo-
functionality with the target polymer matrices is important to at- OR OR
CH2
tain a desired coupling effect (Table 1). O Si R" N: + O Si R" NH CH
Azidosilanes with a general formula (CH3O)3SiAR0 ASO2N3 CH2
OR OR CH2
(Fig. 7) have been reported to be highly efficient in coupling min-
n

eral fillers with polyolefin matrices [62–64,125]. Azidosilanes can

also be hydrolyzed thereby forming the reactive silanols which Fig. 8. A proposed coupling reaction between azidosilane-treated fibers and
are able to react with or condense in the fibers. The organofunc- thermoplastic matrices [63].
 Y. Xie et al. / Composites: Part A 41 (2010) 806–819 815

OH the amine-epoxy reaction [46]. The interfacial interactions of DGE-

O O
O O O O
n acted with polyaminosiloxane forming covalent bonds at the inter-
Fig. 9. Molecular structure of epoxy pre-polymer diglycidyl ethers of bisphenol A
(DGEBA).
cessing. In the published literature, the most reported thermosets
for NFPCs are epoxy compounds and unsaturated polyesters
[1,114,127–130].
4.2.1. Reaction with epoxy resin
Bleached soda pulp fibers were modified with several silanes
(3% of APS, MPS, HDS, or MRPS) and then used as a reinforcement
(40 vol.%) for epoxy resin. The results show that APS was the most
efficient in improving the mechanical properties and reducing the
water absorption of the resulting composites [45]. The reaction
kinetics of epoxy pre-polymer diglycidyl ethers of bisphenol A
(DGEBA, as shown in Fig. 9) with APS was systematically studied
using differential scanning calorimetry (DSC), FTIR, and size exclu-
sion chromatography (SEC), indicating that the epoxy is highly
reactive towards the amine group producing an insoluble fraction
after reaction [131]. The insoluble fraction is formed via the gela-
tion of silane ethoxy and methylol groups which are produced by
BA 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 re-
face [132]. Use of a polymerizing accelerator benzyl
dimethylamine (BDMA) increased the reaction rate of the epoxy
resin and polyaminosiloxane. The coupling mechanism of amino-
silanes in the fiber/epoxy composites have been proposed by sev-
eral 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 compos-
ites [133]. Sisal fiber/epoxy composites (40 vol.% of fiber) coupled
with 5% APS showed a considerable improvement in the compres-
sion strength and wet tensile strength [19].
4.2.2. Reaction with polyester resin
The vinylsilanes have been demonstrated to be able to effi-
ciently 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 ini-
tiated 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

O H O CH2 CH
H
O Si (CH2)3 N 2 H2C C O Si (CH2)3 N
O H O O CH2 CH

OH
APS grafted fiber epoxy resin

Fig. 10. Coupling reaction between APS-grafted natural fiber with epoxy resin.
O C CH CH C O
O

CH2
O O HC
O Si (CH2)3 O C C CH2 + m +
O CH3
O

peroxide

MPS grafted fiber Styrene UP resin

O C CH CH
O

O O
O Si (CH2)3 O C CH CH2 CH CH2
n
O CH3
CH2
O
C O

Fig. 11. Reaction of MPS-grafted fiber with unsaturated polyester resin in the presence of a peroxide initiator.
816 Y. Xie et al. / Composites: Part A 41 (2010) 806–819
(60 wt.% in styrene) with benzoyl peroxide used as a free radical
initiator [45]. Treatment with APS caused a slight increase in the
tensile Young’s modulus of the composite, but did not change the
other mechanical properties. The results are consistent with a pre-
vious study [134]. This is due to the lack of reactivity between the
amino groups of APS and the polyester matrix. In contrast to APS,
treatment of fibers with MPS improved the flexural strength of
the resulting composites and slightly reduced the water uptake
in a 4-week water immersion test [45].
Compared to bleached soda pulp fibers [45], the application of
MPS (1–5%) to the other types of natural fibers such as fique and
sisal fibers resulted in an enhancement in the mechanical proper-
ties of the resulting UP matrix composites. In the presence of the
radical initiator methyl ethyl ketone peroxide (MEKP), the tensile
strength and modulus of the fique fiber/UP composite increase
up to 60% and 80%, respectively, due to the MPS treatment of fibers
[135]. The flexural strength of sisal/UP composites can be im-
proved up to 63% [20]. Comparably, the tensile strength of pineap-
ple leaf fiber (PALF)/UP composites coupled with VTS increased
40% as compared to the uncoupled composites [134]. Dynamic
mechanical analysis (DMA) showed that treatment of banana fi-
bers with MPS or VTS caused an increase in the dynamic storage
modulus and a reduction in the damping value of the resulting
polyester composites, suggesting the interfacial adhesion between
banana fiber and the polyester is improved [54,136]. The varying
mechanical improvement due to the different fiber types after
treatment with MPS may be due to the different fiber constituents
and preparation methods of composites in the studies.
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 con-
tents. 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 fad-
ing and erosion, warpage, mold growth, fungal decay, and strength
loss after a long-term exposure to an external environment
[21,139–144]. These issues are mostly associated with the mois-
ture 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 mois-
ture either through damage or cutting of the composite. Conse-
quently, hydrophobation treatments of fibers thereby reducing
the moisture sorption are of importance for the NFPCs during envi-
ronmental exposure in order to reduce potential damage associ-
ated with water.
Oil palm fibers modified with VTS in an alcohol–wax mixture
(60:40) were soaked in water at different temperatures (30, 50,
70, and 90 °C) to determine their water uptake behavior and the re-
sults showed that VTS-treatment reduced the water uptake of fi-
bers 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 sus-
ceptibility 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 composite’s prop-
erties 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 con-
tent of 6%, less than the 12% observed with the unmodified com-
posites. 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 com-
posites 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 (sol–gel
process) at a specific pH and temperature. The hydrogen bonds
formed between the adsorbed silanols and hydroxyl groups of nat-
ural fibers may be further converted into covalent bonds by heat-
ing 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 organo-
functionalities of silanes and the matrices is required. For the ‘‘in-
ert” 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 fi-
bers with silane can increase the interfacial adhesion to the target
polymer matrices and improve the mechanical and outdoor perfor-
mance of the resulting fiber/polymer composites.
Acknowledgement
The author Dr. Yanjun Xie would like to thank the German Aca-
demic Exchange Service (DAAD) for a research grant support.
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