Composites: Part A 140 (2021) 106171

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Composites Part A
journal homepage: www.elsevier.com/locate/compositesa

Chemical modification of natural fibres to epoxy laminate for

lightweight constructions
Weronika Gieparda a, *, Szymon Rojewski a, Sven Wüstenhagen b, Anna Kicinska-Jakubowska a,
Andreas Krombholz b
a
Institute of Natural Fibres & Medicinal Plants, ul. Wojska Polskiego 71B, 60-630 Poznan, Poland
b
Fraunhofer Institute for Microstructure of Materials and Systems IMWS, Walter-Hülse-Straße 1, 06120 Halle (Saale), Germany

A R T I C L E I N F O A B S T R A C T

Keywords: The aim was to modify products made of natural fibres in order to reduce the composite porosity, reduce
A. Biocomposite flammability and improve the mechanical properties of epoxy laminates. In order to obtain desired properties
A. Fabrics/textiles chemical modification of roving and fabric with use of silanization and flame retardant treatment was conducted.
A. Laminates
For this purpose different types of silanes and flame retardant compounds were used. Flammability of prepared
B. Flame/fire retardancy
fibre - samples were tested by microcalorimeter (PCFC). In the effect of natural fibres modifications flammability
of reinforcing fibres was reduced even by 400%. Investigations of porosity in natural fibre composites were
carried out by X-ray tomography. Improvements of composites flammability was tested according to UL94.
Mechanical tests with quasi-static loads according to DIN EN ISO 178 were carried out, to identify optimized
modifications in fibre and matrix. By combining flame retardancy and improvement of fibre impregnation, one of
the modifications is showing promisingly results.

1. Introduction
Biodegradability and environmentally friendly character of plant
fibres decides about their application for green composite production.
As a renewable resource, natural fibres are used for manufacturing of
recyclable “green” products in industrial processes leading to reduction
of carbon emission and minimizing waste. Flax fibres are used mainly for
textile production (83%), paper (9%), and composites (6%). The in­
crease of natural fibres in reinforced composites is related to replace­
ment of glass fibres. Actual the most popular use of natural fibres is very
short fibres randomly distributed in thermoplastic polymer matrix.
Technologies for processing long flax fibres to unlock the full light
weight potential of natural fibres needs to be developed.
The main limitations for flax in composite are its strong hydrophilic
properties and tendency to porosity in laminate. Non-compatibility
problem in NFC is caused by the polarity difference of natural fibres
and polymer matrix. Composite matrix is hydrophobic and natural fibres
are a hydrophilic material. As result observed was ineffective stress
transfer throughout the interface of the composites due to the poor
adhesion [1,2]. Problem can be solved by applying proper modifications
for natural fibres to change their polarity. Chemical modification
methods used for natural fibres are e.g. mercerization, acetylation,
acrylation, benzoylation, silanization and modification with the use of
carboxylic acids.
• In mercerization, fibres are subjected to NaOH solution resulting to
broken hydrogen bonds, what boosts reactivity of cellulose. Thus
fibres are more receptive for further modifications and have
increased breaking tenacity [3–6].
• Acetylation is carried out by subjecting fibres to acetic anhydride.
Acetylation is the most commonly used process which leads to the
reduction of hygroscopic properties of fibres and improvement in
adhesiveness with polymer matrix [7–9].
• Acrylation is carried out with the acrylic acid after prior merceri­
zation. As the result of acrylation, water adsorption is reduced, yet
this modification does not improve the composite strength [10].
• Benzoylation is carried out with benzoyl chloride. This modification
increases the hydrophobicity and improves the adhesion with the
polymer matrix [11].
• Carboxylic acids modification of natural fibres is carried out with
application of carboxylic acids and leads to an increase in hydro­
phobicity [12].

* Corresponding author.
E-mail address: Weronika.gieparda@iwnirz.pl (W. Gieparda).

https://doi.org/10.1016/j.compositesa.2020.106171
Received 21 July 2020; Received in revised form 28 September 2020; Accepted 15 October 2020
Available online 22 October 2020
1359-835X/© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
W. Gieparda et al.
• Silanization process gives possibility of using more complex re­
actants than simple ones used in modification described above. It is
possible to get additional benefit depending on structure of silane
used for modification, what leads to obtaining better adhesion,
thermal stability and mechanical parameters of the composite
structure [13].
The chemical modification methods related to natural fibres causes
changes in other parameters of composites by the application of various
substituents and functional groups, depending on expected result. In the
textile industry most of the chemical processes used for natural fibres are
limited to mercerization and until recently also acetylation. Both
methods are effective for pre-treatment of the fabric finishing processes,
such as dyeing or softening of fabric, however, applied compounds are
not capable of a permanent bonding with the surface of the lignocellu­
losic material. In the literature usually come across a description relating
to the modification of fibres in the short form, which are in use to pre­
pare composites in the form of granulates or in the form of nonwovens or
fabrics. The composites are prepared by pressing them between ther­
moplastic polymer layers or by padding them with resin and then cross-
linking for hardening in the shape of final product.
The modification used in conducted research was silanization, which
was carried out with newly developed compounds. (This method can
make fibres compatible with composite matrix and improve the strength
of fibres by creating additional bonds between silanes.) Interfacial
bonding mechanisms of silanes should cause improvement of mechan­
ical performance and thermal stability. Condensation between the si­
lanes and –OH groups on the cellulose fibre surface takes place, and a
polysiloxane layer bonded to the cellulose surface is formed. The flame
retardant efficiency of silanes is due to the presence of silicon in their
chemical structure. Therefore, silanization of flax fibers, in addition to
increasing the thermal stability of the fibers, also reduces their
flammability.
Silanization of natural fibres is beneficial in terms of improving the
water resistance of fibres, enhance the wettability of the natural fibres
surface by polymers (mainly non-polar polymers) and promote interfa­
cial adhesion.
Compounds that are often used in various plastic applications are
carbofunctional silanes (CFS). These are compounds of the general for­
mula XnSi (R’Y)4-n, where: X - a functional group sensitive to hydrolysis
(Cl, OR, OCOR), Y - a functional group, e.g. NH2, Cl, OH, OCOR, and R’-
alkylene chain, usually composed of three methylene groups. CFS are
usually called silane coupling agents (SCA) due to the presence of two
functional groups X and Y. CFS form chemical bonds with inorganic
materials as a result of the reaction of functional groups X, while
Flax fabric with plain weave made Flax fabric with plain weave made
of flax warp yarn 68 tex and roving of flax warp yarn 68 tex and roving
400 tex (raw) as a weft. 2000 tex (raw) as a weft.
Fig. 1. Fabrics made of rovings 400, 2000 tex (raw) and 2000 tex (bleached).
2
Composites Part A 140 (2021) 106171
functional groups Y can react with polymers organic [14].
Although silanization alone can significantly reduce flammability, it
is worth to improve this effect further with introducing fire retardants
(FR) into the composite. For improvement of the discussed parameters
several FR’s are offered – from polyphosphates, magnesium hydroxide,
silica, to nanoparticles such as carbon nanotubes (CNT) [15–25]. Every
flammability reducing method has a different mechanism and this cre­
ates a possibility of combining modified natural fibres with several FR’s
for investigation of their efficiency and the interactions between them.
Fibre composites with so called conventional filaments, like types of
glass or carbon fibre are established in different branches, because they
allow formation of lightweight constructions in different technologies.
Pre-impregnation of fibre reinforcement was established, to give robust
processing, up to energy efficient Out of Autoclave consolidation of
laminates.
Synthetic epoxies based on petrochemicals are well established. Thay
have several useful properties such as high tensile strength and modulus,
good adhesion and insulation property, and excellent chemical corro­
sion resistance. Among the various polymer matrices available, epoxy
resins remain dominant in the development of high performance ma­
terials due to their thermal stability, mechanical properties, and pro­
cessability. The cured epoxy resins have highly crosslinked networks
that show high modulus and fracture strength, low creep, and good
performance at elevated temperatures [26–28]. Native epoxies based on
fatty acid ester are available in small scales. Under use of methods for
mathematical classification one can show mutagenic attributes on both
of this types of epoxides, whereby primary epoxides always showing
mutagenic structures. Secondary epoxies, e.g. the fatty acid ester from
Vernonia galamensis is regularly showing not mutagenic attributes [29].
Oilseeds like Lallemantia Iberica and Linum isitatissimum are giving
around 750 kg/ha of oil. In charge of availability in European regions a
new linseed oil based epoxy was developed for our studies.
By its specific low density, natural fibres show comparable me­
chanical properties to types of glass fibre in laminate construction.
Porosity in natural fibre prepregs is well known and actual handled by
high pressure during consolidation or processing in Resin Transfer
Technologies. Combining chemical modifications on fibre with modifi­
cations in matrix-polymer should improve the fibre - matrix interaction
during processing and use-phase of Natural Fibre Composites.
In this paper an innovative chemical modification of natural fibres in
the form of roving on bobbin as well as in the form of fabrics is pre­
sented. Fibres treatment with silane and combination of conventional
halogen-free flame retardant compounds, in fibre and in matrix-
polymer, was carried out for reducing flammability and improving
mechanical properties by reducing composites porosity as a result of
Flax fabric with plain weave made
of flax warp yarn 68 tex and roving
2000 tex (bleached) as a weft.
W. Gieparda et al.
Table 1
Chemical composition of the tested materials unmodified and modified by silanes only (without FRs).
Sample
FFab400
FFab2000
FFab2000bl
FFab400-AmSil.5
FFab2000-AmSil.5
FFab2000bl-AmSil.5
FFab400-VinSil.5
FFab2000-VinSil.1
FFab2000-VinSil.2
FFab2000-VinSil.3
FFab2000-VinSil.4
FFab2000-VinSil.5
FFab2000bl-VinSil.5
FRov400
FRov2000
FRov2000bl
FRov400-AmSil.5
FRov2000-AmSil.5
FRov2000bl-AmSil.5
FRov400-VinSil.5
FRov2000-VinSil.5
FRov2000bl-VinSil.5
FRov2000-AmSil.5/hp
FRov2000-VinSil.5/hp
FRov2000bl-AmSil.5/hp
FRov2000bl-VinSil.5/hp
Table 2
Chemical composition of the tested materials modified by vinylsilane and flame
retardants.
Sample
FFab2000-VinSil.1/APP.5
FFab2000 -VinSil.1/MPP.5
FFab2000 -VinSil.1/PER.5
FFab2000 -VinSil.1/GC.5
Table 3
List of samples to obtain laminates.
1st round silanization
2nd round silanization
Optimizing silanization
Optimizing Flame Retardants
Composites Part A 140 (2021) 106171
The form of natural fibres AmSil VinSil Other
% %
Flax fabric made of roving 400 tex – –
Flax fabric made of roving 2000 tex – –
Flax fabric made of bleached roving 2000 tex – –
Flax fabric made of roving 400 tex 5 –
Flax fabric made of roving 2000 tex 5 –
Flax fabric made of bleached roving 2000 tex 5 –
Flax fabric made of roving 400 tex – 5
Flax fabric made of roving 2000 tex – 1
Flax fabric made of roving 2000 tex – 2
Flax fabric made of roving 2000 tex – 3
Flax fabric made of roving 2000 tex – 4
Flax fabric made of roving 2000 tex – 5
Flax fabric made of bleached roving 2000 tex – 5
Flax roving 400 tex – –
Flax roving 2000 tex – –
Flax bleached roving 2000 tex – –
Flax roving 400 tex 5 –
Flax roving 2000 tex 5 –
Flax bleached roving 2000 tex 5 –
Flax roving 400 tex – 5
Flax roving 2000 tex – 5
Flax bleached roving 2000 tex – 5
Flax roving 2000 tex 5 – High pressure/temp.
Flax roving 2000 tex – 5
Flax bleached roving 2000 tex 5 –
Flax bleached roving 2000 tex – 5
proper polymer penetration between fibres.
2. Materials and methods
VinSil APP MPP PER GC 2.1. Materials
% % % % %
1 5 – – – Flax fibre products: rovings with linear mass 400 tex, 2000 tex (raw)
1 – 5 – – and 2000 tex (bleached) prepared by Safilin Sp. z o.o. and fabrics made
1 – – 5 – of mentioned above rovings prepared by Łukasiewicz Research Network
1 5
– – –
– Textile Research Institute.
Reagents for silanization: Ethyl alcohol 96% pure p.a. supplied by
Sample Matrix/Fibre % (w/w) Resin/APP
% (w/w)
ER.FRov2000bl-VinSil.5 40/60
ER.FRov2000-VinSil.5 50/50
ER.FRov2000bl-AmSil.5 50/50
ER.FRov2000-AmSil.5 40/60
ER.FFab2000-AmSil.5 50/50
ER.FFab2000-VinSil.5 50/50
ER.FRov2000 50/50
ER.FRov2000bl 50/50
ER.FRov2000bl-AmSil.5/hp 50/50
ER.FRov2000-AmSil.5/hp 50/50
ER.FRov2000bl-VinSil.5/hp 50/50
ER.FRov2000-VinSil.5/hp 50/50
ER.30APP.FFab2000-VinSil.1 50/50 30
ER.30APP.FFab2000-VinSil.2 50/50 30
ER.30APP.FFab2000-VinSil.3 50/50 30
ER.30APP.FFab2000-VinSil.4 50/50 30
ER.30APP.FFab2000-VinSil.5 50/50 30
ER.30APP.FFab2000bl-VinSil.1 50/50 30
ER.30APP.FFab2000-VinSil.1/APP.5 50/50 30
ER.30APP.FFab2000-VinSil.1/GC.5 50/50 30
ER.30APP.FFab2000-VinSil.1/MPP.5 50/50 30
ER.30APP.FFab2000-VinSil.1/PER.5 50/50 30
3
W. Gieparda et al. Composites Part A 140 (2021) 106171

HRR for layers for roving 400 tex modified by HRR for layers for roving 400 tex modified by
AmSil VinSil
200 200

150 150

HRR [W/g]
HRR [W/g]

100 100

50 50

0 0
200 250 300 350 400 450 500 550 600 200 250 300 350 400 450 500 550 600
temperature °C temperature °C

FRov400-AmSil.5-1 FRov400-AmSil.5-2 FRov400-VinSil.5-1 FRov400-VinSil.5-2

FRov400-AmSil.5-3 FRov400-AmSil.5-4 FRov400-VinSil.5-3 FRov400-VinSil.5-4

HRR for layers for roving 2000 tex modified by HRR for layers for roving 2000 tex modified by
AmSil VinSil
200 200

150 150
HRR [Wg]

HRR [W/g]
100 100

50 50

0 0
200 250 300 350 400 450 500 550 600 200 250 300 350 400 450 500 550 600
temperature °C temperature °C
FRov2000-AmSil.5-1 FRov2000-AmSil.5-2 FRov2000-VinSil.5-1 FRov2000-VinSil.5-2
FRov2000-AmSil.5-3 FRov2000-AmSil.5-4 FRov2000-VinSil.5-3 FRov2000-VinSil.5-4

Fig. 2. Results of PCFC tests for individual layers of roving (whole bobbins) after the silanization process.

POCH®, 3 - (diethylenetriamine) propyltrimethoxysilane (AmSil) pro­
vided by Unisil Sp. z o.o., vinyl trimethoxysilane (VinSil) provided by
Unisil Sp. z o.o.
Flame retardant compounds: ammonium polyphosphate Exolit AP
423 (APP) supplied by Clariant International Ltd., guanidinium car­
bonate (GC) supplied by Merck Poland Sp. z o.o. with purity of 99%;
pentaerythritol (PER) provided by Sigma-Aldrich® with purity of 98%
and melamine polyphosphate (MPP) supplied by “Alwernia” S.A., Ciech
S.A.
The matrix-polymer (ER) consists of epoxidized linseed-oil provided
by Traditem GmbH, 40,721 Hilden and a specific compound of cross­
linking agents: Citric Acid monohydrate 99,0–102,0% via Alfa Aesar®
and Maleic Acid 99% provided by Acros Organics. The flame retardant
compound used in matrix-polymer is ammonium polyphosphate (APP),
provided by WTH GmbH, D-21682 Stade.
2.2. Rovings and fabrics preparation
In order to develop a fabric structure that minimizes the porosity of
the composite, linear flax fibre materials were developed and produced
at first: rovings with a linear mass of 400 tex, 2000 tex (raw) and 2000
tex (bleached). The process of preparing the rovings included long fibre
scutching, preparation for combing flax, combing flax, preparation of
combed sliver, preparation of rovings and bleaching of the rovings.
Next, from rovings flax fabrics with plain weave were produced. Warp
was a yarn with a linear mass of 68 tex, and weft rovings: 400 and 2000
tex (raw), 2000 tex (bleached). Fig. 1 presents the fabrics.
2.3. Modification of rovings and fabrics
For the study two types of silanes with different structure and
properties were used - more polar, nitrogen containing aminosilane and
less polar vinylsilane. The work started with the parameter adjustment
for rovings and fabrics modification method. Due to the susceptibility to
rapid hydrolysis of the silanes, and then polymerization of the com­
pound in aqueous solution, silanization process was carried out in a
mixture of water with ethanol in acidic medium (acetic acid). Parame­
ters of modification process such as: pH, solution concentration and
modification time, were adjusted: 5% (w/w) silane (AmSil or VinSil)
(Table 1), appropriate amount of FR (Table 2), solution in C2H5OH/H2O
(6/4) (v/v) with pH = 4,5. Modification was conducted for 4 h in room
temperature. After that the tested materials were drained and placed in
chamber set at 40 ◦ C. Dry materials in the form of rovings and fabrics
were cured for 10 min at 105 ◦ C. The parameters of the modifications
process were optimized during studies in order to minimize fibres
damage, and for obtaining the highest reactivity and achieving the best
yield of the silanization process. In the course of research, the amount of
silane was reduced to 1%.
2.4. Laminate preparation
Under aspects of reduced flammability and optimized impregnation

4
W. Gieparda et al. Composites Part A 140 (2021) 106171

HRR for unmodified fabrics HRR for fabrics made of roving 2000 tex modified
by AmSil or VinSil
250 250
200 200
HRR [W/g]

HRR [W/g]
150 150
100 100
50 50
0 0
200 250 300 350 400 450 500 550 600 200 250 300 350 400 450 500 550 600
temperature [°C] temperature [°C]
warp FFab400 FFab2000 FFab2000-AmSil.5
FFab2000 FFab2000bl FFab2000-VinSil.5

HRR for fabrics made of roving 400 tex modified HRR for fabrics made of bleached roving 2000 tex
by AmSil or VinSil modified by AmSil or VinSil
250 250
200 200

HRR [W/g]
HRR [W/g]

150 150
100 100
50 50
0 0
200 250 300 350 400 450 500 550 600 200 250 300 350 400 450 500 550 600
temperature [°C] temperature [°C]
FFab400 FFab400-AmSil.5 FFab2000bl FFab2000bl-AmSil.5
FFab400-VinSil.5 FFab2000bl-VinSil.5

Fig. 3. Results of PCFC tests for fabrics before and after the silanization process.

rovings and unidirectional fabrics were pre-impregnated with matrix-
polymer (ER) in a laboratory scale. Fibre - samples were used as unidi­
rectional layer (Table 3). To guarantee the reproducibility of matrix to
fibre ratio in compacted laminates, according to DIN EN 2332 the resin
flow was tested. The optimum fibre to matrix ratio was validated by
mechanical tests on compacted laminates according to DIN EN ISO 178.
In correlation to literature [30] the fibre content of 50% (w/w) in out-of-
autoclave compacting laminates is optimum.
2.5. Methods
2.5.1. Flammability tests of fibre
Flammability tests were carried out by pyrolysis combustion flow
calorimeter (PCFC) from FTT. Tests were performed according to the
standard of ASTM D7309-2007. The heating rate was 1 ◦ C/s. Pyrolysis
temperature range was 75–750 ◦ C, and the combustion temperature was
900 ◦ C. The flow was a mixture of O2/N2 20/80 cm3/min and the sample

HRR for layers for roving 2000 tex modified HRR for layers for roving 2000 tex modified under
under high press. by AmSil high press. by VinSil
200 200

150 150
HRR [W/g]

HRR [W/g]

100 100

50 50

0 0
200 250 300 350 400 450 500 550 600 200 250 300 350 400 450 500 550 600
temperature °C temperature °C
FRov2000-AmSil.5/hp-1 FRov2000-VinSil.5/hp-1
FRov2000-AmSil.5/hp-2 FRov2000-VinSil.5/hp-2
FRov2000-AmSil.5/hp-3 FRov2000-VinSil.5/hp-3

Fig. 4. The results of PCFC tests for individual layers of roving (whole bobbins) after the silanization process under high pressure and temperature.

5
W. Gieparda et al. Composites Part A 140 (2021) 106171

flame. Samples in dimension 80 × 10 × 4 mm (milled from plate of

HRR for fabrics made of roving 2000 tex modified by VinSil and FRs laminate) were prepared under standard climate condition 48 h, 23 ◦ C,
250 50 rel. humidity. Prepared samples were exposed in horizontal and
vertical orientation and time 30 s. Burntime (s), drips of particles and
200 length of burn (mm) at the samples were determined and used for
HRR [W/g]

classification.
150

100 2.5.3. Porosity tests of laminate

Content of porosity in laminates was determined by non-destructive
50 method 3D X-ray computer tomography, using a RayScan 200E (Ray­
Scan Technologies GmbH). The size of voxel was chose as 9,24 µm,
0
voltage at X-ray tube 100 kV at electric current 130 µA and a shutter
200 300 400 500 600
time of 1500 ms for 1440 projections on each samples. The samples were
temperature [°C] prepared from specific laminates. Region of interest is middle part of
each sample. Automated determination of porosity was used.
FFab2000-VinSil.1 FFab2000 -VinSil.1/MPP.5
FFab2000 -VinSil.1/GC.5 FFab2000-VinSil.1/APP.5 2.5.4. Mechanical tests of laminate
In accordance to DIN EN ISO 178 (04/2006) mechanical character­
FFab2000 -VinSil.1/PER.5
ization in quasi-static 3 point bending test was carried out. Used testing
machine was calibrated Z050 (Zwick/Roell GmbH & Co. KG). Samples in
Fig. 5. Results of PCFC tests for fabrics made of roving 2000 tex modified with
dimension 80 × 10 × 4 mm (milled from plate of laminate) were pre­
1% of vinylsilane and selected flame retardant compounds.
pared under standard climate condition 24 h, 23 ◦ C, 50 rel. humidity.
Measuring of distance was carried out with MultiXtens MM (maximum
weight was 3–4 (±0,01) mg. The heat release temperature (Tmax), error ± 1 µm) and measuring of force with calibrated 1 kN load-cell at a
maximum heat release rate (HRRmax), time at which HRRmax occurs speed of 2 mm/min till break of samples. The samples were positioned
(tmax) were determined. on free support with distance of 64 mm and radius of 5 mm.

2.5.2. Flammability tests of laminate 3. Results and discussion

Flammability tests on laminate were carried out in a burning
chamber Wazau GmbH Type BBK. Tests were performed according to 3.1. Modification of rovings
UL94 method. The flammability was determined in horizontal and
vertical orientation of samples. Used ignition flame was 50 W propane In the first stage of the research, modification of rovings was carried

ER.FRov2000bl-AmSil.5 ER.FRov2000-AmSil.5

X-ray computer tomography, square section. X-ray computer tomography, square section.
No automated porosity measurement possible. No automated porosity measurement possible.
ER.FRov2000bl-VinSil.5 ER.FRov2000-VinSil.5

X-ray computer tomography, square section. X-ray computer tomography, square section.
ER.FRov2000bl-AmSiI.5 porosity diameter [mm] ER.FRov2000-AmSiI.5 porosity diameter [mm]
over sphericity over sphericity

15 15

10 10

5 5

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
sphericity sphericity

Determined porosity diameter over sphericity. Determined porosity diameter over sphericity.

Fig. 6. Porosities in out-of-autoclave compacted laminates with different types of modification in fibre, unmodified matrix-resin.

6
W. Gieparda et al. Composites Part A 140 (2021) 106171

Laminate: ER.FFab2000-VinSil.1/APP.5, 30 % w/w Laminate: ER.FRov2000-VinSil.5, unmodified epoxy

APP in epoxy resin. resin.

Square section as instance of automated volume Square section as instance of automated volume
porosity [mm³] 0 … 4,78 mm³ from X-ray computer porosity [mm³] 0 … 4,78 mm³ from X-ray computer
tomography. tomography.

ER.FFab2000-VinSil.1/APP.5, 30% APP in ER.FRov2000-VinSil.5, unmodified epoxy resin

epoxy resin porosity diameter [mm] over porosity diameter [mm] over sphericity of
sphericity of pores pores

15 15

10 10

5 5

0 0
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8
sphericity sphericity

Estimated porosity diameter over sphericity. Estimated porosity diameter over sphericity.

Fig. 7. Porosities in laminates with different types of silane modification of fibre - samples and modified or unmodified matrix resin. Decrease of pore-volume was
estimated in composite within flame retardant APP in epoxy resin. Volume based porosity is around 10%.

Mechanical properties of laminates with unmodified epoxy Mechanical properties of laminates with fibre samples
resin impregnated under high pressure conditions and
10000 unmodified epoxy resin
9000 10000
8000 9000
7000 8000
E_f [MPa]

7000
E_f [MPa]

6000 6000
5000 5000
4000 4000
3000 3000
2000 2000
1000 1000
0
0

3 pt bending
3 pt bending

Fig. 8. The effect of aminosilane and vinylsilane impregnation under atmo­

Fig. 9. The effect of aminosilane and vinylsilane impregnation under high
spheric pressure on laminates prepared of bleached and raw rovings and uni­
pressure on laminates prepared of bleached and raw rovings with unmodified
directional fabric with unmodified epoxy resin compared by E-module.
epoxy resin compared by E-module. The rovings were taken from outer layer
of bobbin.
out. Rovings were prepared in a way that should give possibility to
modifying them in entire volume. These preparations included the
similar for all types of modified roving. A notable reduction in flam­
replacement of full bobbins with perforated ones and rewinding to
mability was observed in the outer layer of roving, while in subsequent
provide a looser structure of the bobbins. The entire bobbins of roving
layers (2, 3, and 4) flammability remains comparable to roving before
were subjected to the process of silanization with set parameters. To
the modification process. In this case, the “filter” effect was observed. It
assess the homogeneity of the modified rovings, four layers were
was due to the fact that roving layers exposed directly to silane filtered
selected from each bobbin. The outer layer of the roving is layer 1,
the modifying solution, due to which the inner roving layers were
middle layers – 2 and 3 and the inner layer is layer 4.
exposed to a lower concentration solution.
Flammability results, which were presented on the Fig. 2 were

7
W. Gieparda et al.
Yarn 2000 tex bleached (Row 1) and unbleached, graded
silanisation VinSil [%] and 30% (w/w) APP in matrix-polymer
12000
11000
10000
9000
8000
E_f [MPa]
7000
6000
5000
4000
3000
2000
1000
0
3 pt bending
Fig. 10. The mechanical effect of graded silanization conducted under atmo­
spheric pressure o laminates prepared of unidirectional fabrics made from
bleached (Row 1) and raw rovings and epoxy resin modified with 30% (w/w) of
APP, compared by E-module.
3.2. Modification of flax fabrics
In the next stage, modification of fabrics made of rovings as weft with
linear mass 400, 2000 and 2000 tex (bleached) were carried out. The
Fig. 3 presents the results of PCFC tests regarding the flammability of
individual fabrics before and after the process of their modification with
a 5% solution of aminosilane and vinylsilane.
Reduction of flammability of fabrics as a result of their modification
with silanes was insignificant. A difference, that is noteworthy, was
observed only in the case of bleached fabric made of bleached roving
with linear mass 2000 tex, modified with aminosilane. In this case, there
was a 33% reduction in the flammability of the fabric. The fire retard­
ancy effect was obtained thanks to the application of a silane with
appropriate structure. Aminosilane limited fibres flammability due to
the content of nitrogen (in NH2 group). The high content of nitrogen in
used aminosilane (three amino groups in one molecule) might have been
linked to the decrease flammability [31,32].
3.3. High-pressure modification of flax rovings
The next stage of research was the development of an innovative
process for high-pressure chemical modification of flax fibres, in the
form of roving and fabrics, using the silanization method. The process
was carried out using an autoclave under high temperature and pres­
sure. Other parameters of the modification process remained un­
changed. In this case, only three layers from the entire bobbin were
selected to assess the homogeneity and flammability of modified rovings
(outer layer – 1, middle layer – 2, inner layer – 3).
The process was carried out under high pressure and temperature in
order to obtain uniform modification of the entire roving bobbin. High
pressure facilitates the penetration of subsequent layers of roving. A
reduction in flammability, presented on the Fig. 4, was observed for the
outer and inner layers, while the middle layer in each case showed no
reduction. As it took place in case of rovings modified at high pressure,
the “filter effect” can be observed also under high pressure conditions.
The reason to observe greater flammability decrease of the inner layers
in comparison with high pressure conditions is fact that rovings have
perforated bobbin which gave the modifying solution possibility of
penetration while conducting modification process under high pressure
condition. Despite the parameters used, it was not possible to achieve
uniform application of the solution throughout the entire volume of
roving.
8
Composites Part A 140 (2021) 106171
3.4. Modification of rovings and flax fabrics with flame retardant
compounds addition
The next stage of research was the introduction of additional flame
retardants into the modification process to further reduction of the
flammability of both flax fabric and the finished product. The four
different types of flame retardant compounds were selected: ammonium
polyphosphate Exolit AP 423 (APP), guanidinium carbonate (GC),
pentaerythritol (PER) and melamine polyphosphate (MPP). They were
added at a level of 5% by weight.
The concentration of silane used has been reduced to 1%, which has
had a positive effect on reducing the porosity of composites as well as
improving mechanical properties of final samples. Silanes in a concen­
tration above 1% still improves the mechanical properties of the pre­
pregs in comparison with non-modified fabric, however, it causes the
individual fibres to stick together, which makes the proper deposition of
epoxy resin in entire volume of fabric impossible.
The results of PCFC tests for samples modified by 1% vinylsilane and
various FR compounds at a concentration of 5% showed (Fig. 5) that
pentaerythritol used alone did not have a greater effect on the reduction
of fabric flammability. A better effect was noticed in the sample with
melamine polyphosphate as well as guanidine carbonate – a reduction of
the flammability of the fabric at a level of 25–30%. When using
ammonium polyphosphate, the flammability reduction was 400% but
the temperature in which maximum HRR occurs was lower due to the
decomposition of APP which starts around 165 ◦ C into the water,
ammonia and polyphosphoric acid [33]. Polyphosphoric acid splendidy
catalyzes dehydration reaction of hemp fibers to form a char, especially
in the presence of a nitrogen-containing silane [34]. This type of result
has been shown in many other publications.
3.5. Silanization of fibre effecting porosity of laminates
The used silanes in fibre modification showed different porosities in
laminate produced out-of-autoclave. Results of X-ray CT (Fig. 6) showed
a lower porosity in ER.FRov2000bl-VinSil.5 and ER.FRov2000-VinSil.5
compared to ER.FRov2000bl-AmSil.5 and ER.FRov2000-AmSil.5. By
aminosilane (AmSil) modified fibres resulted in a very large amount of
open pores in laminate, so automated determination of porosity was not
usable. For vinylsilane (VinSil) modified fibres the automated charac­
terization of pores showed a wide aspect ratio of pores, with length up to
Mechanical properties of laminates with fabrics made of
raw rovings 2000 tex, 1% (w/w) Vin-Sil, 5% (w/w) flame
retardant and 30% (w/w) APP in matrix
8000
7000
6000
E_f [MPa]
5000
4000
3000
2000
1000
0
3 pt bending
Fig. 11. Effect of different flame retardants and silane modification on lami­
nates prepared of unidirectional fabrics made from raw fibres and epoxy resin
with 30% (w/w) of flame retardant APP, compared by E-module.
W. Gieparda et al. Composites Part A 140 (2021) 106171

UL 94HB ER.30AP ER.30AP ER.30AP ER.30AP ER.30AP ER.30AP

horizontal flammability test

P.FFab20 P.FFab20 P.FFab20 P.FFab20 P.FFab20 P.FFab20
00 bl- 00VinSil. 00VinSil. 00VinSil. 00VinSil. 00VinSil.
VinSil.1 1 2 3 4 5
drying [s] 45 50 100 65 73 burn

v < 40mm/min 0 0 0 0 0

classification HB40 HB40 HB40 HB40 HB40

UL 94HB ER.30APP.F ER.30APP.F ER.30APP.F ER.30APP.F ER.30APP.

horizontal flammability test

Fab2000Vin Fab2000Vin Fab2000Vin Fab2000Vin FFab2000

Sil.1/ Sil.1/ Sil.1/ Sil.1/ VinSil.1
APP.5 GC.5 MPP.5 PER.5
drying [s] 10 20 60 50 45
v < 40mm/min 0 0 0 0 0

classification HB40 HB40 HB40 HB40 HB40

UL 94V ER.30APP.F ER.30APP.F ER.30APP.F ER.30APP.F ER.30APP.

Fab2000Vin Fab2000Vin Fab2000Vin Fab2000Vin FFab2000
flammability test

Sil.1/ Sil.1/ Sil.1/ Sil.1/ VinSil.1

APP.5 GC.5 MPP.5 PER.5
drying [s] 0 60 60 50 burn
vertical

classification V-0 NB NB NB

Fig. 12. Effect of graded silane concentration on laminates with bleached (row 1) and raw (rows 2…6) unidirectional fabrics and epoxy resin with 30% (w/w) APP as
well as the effect of different flame retardants on laminates, compared by UL 94 using 50 W propane flame.

10 mm. Bleached roving 2000 tex showed small decreased aspect ratio
of pores.
In second step porosity of optimized silane modification in roving
ER.FRov2000-VinSil.5 and unidirectional fabric ER.FFab2000-VinSil.1/
APP.5 was investigated (Fig. 7). Hereby the interaction between opti­
mized silanization with unmodified and flame retardant modified epoxy
resin was successful compared by X-ray CT. Automated determination of
porosity showed a 40% reduction of aspect ratio in pores with maximum
length of 6 mm in both types of textile construction: roving layer and
unidirectional fabric.
The higher porosity in composites with aminosilane-modified fabric
was most likely the result of accelerated polymerization of the resin.
This process was accelerated by the presence of amine groups on the
fabric surface, which acted as an additional amount of hardener. A
coating layer was created on the surface of the fabric which prevented
the penetration of epoxy resin into the reinforcement consisted of
several layers of the modified material.
3.6. Mechanical effect of silane modification on bleached and raw fibre
samples
Silanization of bleached and raw rovings examined under atmo­
spheric pressure, didn’t show expected increase of specific E-module
(Fig. 8). In case of raw rovings both type of atmospheric pressure sila­
nization showed slight increase of specific E-Module. In case of bleached
roving the atmospheric pressure vinyl silanization showed lower
decrease of specific E-module, than amin silanization. Unidirectional
fabric silanizated under atmospheric pressure showed reduced me­
chanical performance in comparison to laminate from roving. This may
be induced by silanization of the fabric only as whole structure and by
fibre ondulation from small binding yarns in warp direction of fabric.
Comparing only unidirectional fabrics in laminate (Row 3 and 6 in
Fig. 8) improved mechanical performance by vinylsilane on raw fibre
can be observed. Vinylsilane also showed a lower porosity (Fig. 6). In
case of vinylsilane-modified fabrics, the porosity of the composite
decreased because this silane did not contain groups that could accel­
erate the hardening of the resin. Lower porosity resulted with increased
strength, at the same time the increase in strength compared to un­
modified fabric indicated the interaction of the epoxy used with the
vinyl group present on the surface of the modified fibers.
Silanization of rovings under high pressure condition effected spe­
cific E-modulus what was illustrated on Fig. 9. Unfortunately, silaniza­
tion carried out under high pressure on bobbin leads to inhomogeneous
results in content of silane on fibre. This causes also inhomogeneous
fibre to matrix interaction, resulting in specific E-modules.
3.7. Mechanical effect of graded concentration of silane
To estimate the optimum concentration of vinylsilane on unidirec­
tional fabric a grading of silanization was carried out to prepare lami­
nated samples for 3-point bending test. Regarding the overall needed
improvement of flame retardancy the flame retardant APP was com­
bined with epoxy resin. The APP in epoxy resin doesn’t affect negatively
to E-module. When comparing row 6 (ER.FFab2000-VinSil.5 with E-
module 3.300 MPa) in Fig. 8 with row 6 (ER.30APP.FFab2000-VinSil.5
with E-module 5.727 MPa) in Fig. 10 is visible that APP in epoxy resin
will slightly increase performance of unidirectional fabric. It was also
found that vinylsilane in the concentration of 1% w/w had better effect
on rising the E-module in case of laminate prepared with raw fabric
compared to laminate prepared with bleached one (Row 1 and 2 in
Fig. 10). For following development steps the concentration of 1% (w/
w) of vinylsilane to fibre was chosen, also in respect to flammability tests
of laminates (see point 3.9).
3.8. Mechanical effect of flame retardants on silanized fabric
All observed fabrics modified with flame retardants showed decrease
of the laminates E-modulus (Fig. 11). The laminates were produced with

9
W. Gieparda et al.
unidirectional fabrics (roving 2000 tex raw in weft) modified with
vinylsilane 1% w/w and addition of different flame retardants in 5% (w/
w). Epoxy resin including 30% (w/w) of flame retardant APP was used
for preparation of laminates, which were tested in 3 point bending.
3.9. Flammability tests of laminates
In horizontal flammability test according to UL 94 both types of si­
lanes were effective in low concentration of 1% w/w in fibre, when APP
was used as flame retardant in epoxy resin. The better adhesion between
the fabric after silanization with vinylsilane and epoxy matrix compared
to laminates with the unmodified fabric led to additional reduction of
the composites flammability. According to literature reports, poorer
adhesion between the natural fibers and polymer matrix could redound
to an increase in combustion rate of composites [35].
For further improvements in combination with vinylsilane 1% (w/w)
different flame retardants in amount of 5% (w/w) where added on fil­
aments and also tested according to UL 94. The results of flammability
tests intending the use of flame retardant APP in combination with
minimal silanization 1% (w/w) of vinylsilane. When using APP in fibre
impregnation and in epoxy resin the lowest flammability in horizontal
and vertical flammability test was reached (Fig. 12).
4. Conclusions
The aim of the study was to improve mechanical properties and
reduce the flammability of prepregs using chemically modified rein­
forcing material. It was possible to successfully modify rovings with
various linear mass and flax fabrics made of these rovings and obtain
lignocellulosic material with improved adhesion to epoxy resin.
The use of aminosilane (AmSil) was better in the field of flamma­
bility reduction of natural fibres, however the greatest effectiveness of
the modification in field of improving mechanical properties in laminate
was obtained with the use of vinylsilane (VinSil). More uniform and
efficacious fibres modification was obtained with fabric modification
than with roving, what was an succession of “filter effect” occurring
during the modification process of rovings (even under high pressure
conditions). Modified fabric materials proved to be much more effective
in the context of application to composites. To improve the mechanical
properties different concentration of vinylsilane were used. Simulta­
neously the research on further reduction of flammability of fabric and
resin were carried out with use of number flame retardant compounds.
The best result was obtained for laminates prepared of raw flax fabric
made of roving 2000 tex modified with vinylsilane (1% w/w) and APP
(5% w/w) and epoxy resin with additional 30% (w/w) of APP.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The study has been carried out within the Project CORNET /24/1/
2018 – Preimpregnated Flax Fibre Laminate for processing under low
pressure conditions. The project is co-financed by National Centre for
Research and Development within the CORNET Initiative, 2018-2020.
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