Composites Science and Technology 171 (2019) 70–77

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Composites Science and Technology

journal homepage: www.elsevier.com/locate/compscitech

All ‘green’ composites comprising flax fibres and humins' resins T

a,b b,∗ a b
Anna Sangregorio , Nathanael Guigo , Jan C. van der Waal , Nicolas Sbirrazzuoli
a
Avantium Chemicals B.V., Zekeringstraat 29, 1014 BV, Amsterdam, the Netherlands
b
Université Côte d'Azur, Institut de Chimie de Nice, CNRS, UMR 7272, 06108, Nice, France

A R T I C LE I N FO A B S T R A C T

Keywords: The use of all “green” composite materials is a great environmental option for several applications such as
Fibres (A) construction or automotive. A new type of all green composites has been prepared by compression moulding flax
Curing (B) fibres with humins as the matrix. Humins are macromolecular heterogeneous furanic co-products from bior-
Thermomechanical properties (B) efinery operations. For the first time the potential of humins as a whole thermoset-like matrix in combination
Scanning electron microscopy (D)
with natural fibres was studied. The raw industrial humins were cross-linked with and without catalyst. The
Biocomposites
effect of the process conditions on the final properties of the composites was studied. Good tensile properties
were measured by tensile test and Dynamic Mechanical Analysis. Observations of the fracture surface were done
by Scanning Electron Microscope, revealing a void-free morphology. The study finally focused on the water
absorption behaviour, underlining the more hydrophobic nature of the humins' composites compared to the raw
flax mat. The good adhesion between the fibre and the matrix was underlined. Humins interacts with the hy-
drophilic fibres thus creating a good interphase, leading to improved properties. The study demonstrated the
possibility of using a biorefinery co-product as a thermoset matrix for preparing composites materials.

1. Introduction Nonetheless, the majority of commercial applications uses petrochem-

The increase of the sustainability awareness, together with the
rising concerns on depletion of global resources, is leading to a new
interest in environmentally friendly materials. The focus has been put
on the use of lignocellulosic materials, representing one of the largest
renewable raw material resources on the earth. Natural fibres are
therefore a very good candidate for replacing glass and carbon fibres in
composites applications [1–5]. The use of natural fibres for the pro-
duction of composites brings along a number of advantages from an
economical and environmental point of view. These materials show
considerable toughness, flexibility, easy processing, and minimal health
hazard, low cost and easy availability [2,6,7]. This makes this material
the perfect candidate in automotive application and certain structural
applications [4,8–12]. Both thermoset and thermoplastic matrices have
been used together with natural fibres. The most commonly thermo-
plastic matrices commercially used comprise polypropylene (PP),
polyethylene (PE) and polystyrene (PS) [13–16]. Polyesters, epoxies,
and phenolics have been largely used as thermoset resins [17,18]. The
use of biobased alternatives such as polylacticacid (PLA) and poly-
hydroxyalkanoate (PHA) have also been studied [19–23]. More re-
cently, novel biobased matrices have been investigated, such as starch-
based thermoplastics or soybean-based thermosets matrices [24–31].
ical-based resin [14,32–35].
The good properties of composites are usually due to the high
strength and modulus of the fibres, improved by the matrix which
serves as load transfer medium between the two phases. In case of
natural fibres composites, the main drawback of using hydrophobic
matrices with highly hydrophilic natural fibres is exemplified by the
lack of interfacial adhesion [1,14,26,34,36–39]. Good interfacial in-
teractions play a fundamental role in determining the final properties of
the composites, assuring a good stress transfer. Moreover, it would also
protect natural fibres from the environment, avoiding moisture ab-
sorption from the surrounding, gradually decreasing the final properties
[40–42]. To overcome this problem, the common methods used to
improve adhesion between the two phases are by a chemical mod-
ification of the fibre-matrix interface using coupling agents or by
grafting small molecules with hydrophilic chemical groups
[33,39,43–47]. Another possibility is to use a biobased matrix which
can well interact with the hydrophilic groups in natural fibres. For in-
stance, the use of soy protein isolates as matrix leads to natural fibres'
composites with very good interfacial adhesion [24–27,48]. Another
example is the fabrication of all-cellulose composites (ACC) where both
matrix and the reinforcement is constituted of cellulose thus improving
the interfacial adhesion leading to superior mechanical and thermal

∗
Corresponding author.
E-mail address: nathanael.guigo@unice.fr (N. Guigo).

https://doi.org/10.1016/j.compscitech.2018.12.008
Received 3 August 2018; Received in revised form 15 November 2018; Accepted 10 December 2018
Available online 12 December 2018
0266-3538/ © 2018 Elsevier Ltd. All rights reserved.
A. Sangregorio et al.
properties [49,50].
In this context, finding solutions combining environmentally
friendly and sustainable composites and keeping in mind the goal of
improving interfacial adhesion between matrix and filler, has become
an urgency [27,51–53]. Such a solution could be using humins as ma-
trix in natural fibres composites. Humins is an emerging new biobased
material, co-product of sugar conversion process. Humins are hetero-
geneous and polydisperse macromolecules mainly constituted by
furanic rings comprising aldehydes, carboxylic acids and hydroxyls as
main functional groups. Humins valorisation matter is more and more
under the spotlight, thanks to the growing attention of industries in
green chemistry and biomass valorisation [54–60]. Using humins
would lead to numerous advantages: (i) combining humins' matrix with
natural fibres would allow the production of “all green composites”, a
very recent and attractive research line nowadays
[1,27,38,49,51–53,61,62] (ii) the functional groups present on humins
suggest the possibility to obtain a very good affinity with the cellulosic
fibres, solving the problem linked to the use of compatibilizer (iii) using
humins as resin would perfectly fit in the by-product valorisation
concept, providing high-value products from this material.
Humins were shown to be able to crosslink in relatively low tem-
peratures and short times, depending on the thermal treatment used.
These conditions would also affect the final structure and properties of
the humins' resin [58]. The possibility of using humins for composites
elaboration was already demonstrated by Pin et al. [1]. Large quantities
of humins (55 or 75% w/w) were included in a polyfuranic network to
prepare a thermoset matrix for binding cellulosic fibres. Better me-
chanical properties and interfacial adhesion were observed when hu-
mins were included in the polyfurfuryl alcohol network. Accordingly,
this proof of concept could be extended to natural fibre composites
comprising humins as the only reactive matrix.
Therefore, the focus of this work is, for the first time, on the pro-
duction of homogeneous and stable humins/flax fibres composites ob-
tained by compression moulding. No additional resins or compati-
bilizers were employed. Different process conditions were tested and
their effects on the thermo-mechanical properties were highlighted. To
this end, the relaxation behaviour and the thermal stability were stu-
died by means of Dynamic Mechanical Analyses (DMA) and thermo-
gravimetric analyses (TGA). Water absorption behaviour and leaching
tests were done to obtain further insights on the composites. The focus
was set on obtaining samples with good hydrophobic behaviour. The
fracture surface of the composites was observed by scanning electron
microscopy (SEM) to check the morphology at the matrix/fibres inter-
face and to control if good adhesion was obtained.
2. Materials and methods
2.1. Materials
Humins were supplied by Synvina B.V. and produced in their pilot
plant in Geleen, the Netherlands, by conversion of fructose and glucose.
p-Toluenesulfonic acid monohydrate (PTSA) was used as acidic catalyst
to promote humins polymerisation. PTSA was supplied by Sigma
Aldrich, (Mw = 190.22 g/mol, melting point = 103–106 °C, purity >
98.5%). Flax fibres mat were supplied by HempFlex, the Netherlands
and were used as received. The fibres used were a non-woven mat with
a grammage of 600 g/m2. No peculiar treatment was applied to the mat
prior to the impregnation with the humins as attested by the presence of
some remaining waxes or pectins at the surface of flax fibres. The
morphological observation of the mat by means of SEM is shown in
supplementary information.
2.2. Resin and composites preparation
Two formulations of humins' resins were prepared; (i) raw humins
preheated for one hour in the oven at 120 °C and (ii) raw humins which
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Composites Science and Technology 171 (2019) 70–77
were preheated for 20 min at 120 °C before 1.5 %wt of PTSA was added
slowly. The latter humins' mixture was then stirred for 5 min at 120 °C.
The thermal pre-treatment was applied to obtain optimal viscosity
(∼10 Pa s measured by rheometry) to impregnate the fibres. In both
cases, the resin was homogeneously spread over the flax mat and flat-
tened between two non-adhesive films. The composites were prepared
by compression moulding. Two samples obtained with the two resins
were processed at 140 °C for 40 min to study the effect of the catalyst on
the final properties. One more sample was prepared with the PTSA
catalyst and processed at 140 °C for 20 min, to demonstrate the possi-
bility of decrease the time of process when using a catalyst, without
significantly compromising final properties. A pressure of 2 bars was
used for the preparation of all the samples. The weight ratio between
humins and flax was around 40: 60.
2.3. Tensile test
Tensile properties of the composites were tested with an Instron
5565 apparatus in tensile mode with crosshead speed of 3 mm min−1,
with a loadcell of 1 kN. Samples of dimension 40 × 60 × 1.3 mm
(length x width x thickness) were impregnated and cured. The speci-
mens were cut into strips of 40 × 10 × 1.3 mm (length x width x
thickness) for the tensile tests. For each curing condition, six samples
were tested to evaluate the average Young's modulus and maximum
tensile strength.
2.4. Dynamic mechanical analysis (DMA)
The dynamic mechanical properties were studied by dynamic me-
chanical analysis (DMA), Mettler-Toledo DMA-1 in tensile mode.
Samples were tested on temperature sweeps from −40 °C to 150 °C with
a heating rate of 2 °C.min−1. Experiments were done in a single fre-
quency oscillation mode with a frequency of 1 Hz, a force amplitude of
0.1 N and a displacement amplitude of 0.1% in auto tension offset
control. A preload of 1 N was applied.
2.5. Thermogravimetric analysis (TGA)
Thermogravimetric measurements were carried out on a TGA/
DSC3+ from Mettler-Toledo. To study the thermo-oxidative degrada-
tion of composites, measurements were performed at a heating rate of
10 °C.min−1 under air flow (50 mL min−1) from 30 °C to 800 °C. On the
other hand, the thermal degradation and the char yield was rather
highlighted through measurements under nitrogen gas flow
(50 mL min−1) from 30 °C to 1000 °C.
2.6. Scanning electron microscopy (SEM)
The morphology of natural fibre composites after fracture by tensile
test were observed by scanning electron microscopy (SEM) at the mi-
croscopy centre of University Nice Sophia Antipolis using a JEOL 6700F
microscope equipped with a field emission gun. The electron beam
voltage was fixed to 1 kV.
2.7. Water absorption behaviour and leaching test
Water absorption was tested on (i) reference sample cured after
impregnation with raw humins (ii) reference sample cured after im-
pregnation with raw humins and PTSA initiator (iii) reference raw
natural fibres mat. In each case, the weight of the samples was checked
before immersion in water. The sample was then let for a specific in-
terval of time in water. The weight was checked every time the sample
was taken out of the water, and the water was then replaced. The
samples were let in water up to 120 h. Leaching water was collected and
analysed for monomers content using ultra high performance liquid
chromatography (UPLC). UPLC analyses were performed with a column
A. Sangregorio et al.
Waters Acquity UPLC HSS C18, 2.1 × 100 mm, 1.8 μm, equipped with
UV and ELSD detectors.
3. Results and discussion
3.1. Tensile properties
The tensile properties of flax fibres composites depend on several
factors, which can be linked either to the fibres used and/or to the
matrix employed. Concerning the matrix, when using humins' resin it is
important to consider the thermal treatment applied. Indeed, it was
recently demonstrated that depending on the time and temperature of
treatment it is possible to tune the degree of cross-links in humins and
accordingly their glass transition temperatures [58].
Two different resins were tested, humins with and without PTSA
catalyst, to study the effect on the final properties. These two samples
were processed at 140 °C for 40 min. One more sample was prepared at
140 °C for 20 min. This last sample was prepared using PTSA since if no
catalyst is used, curing times below 40 min are not sufficient to fully
cross-link the resin. Indeed, PTSA acts as an acidic initiator for the
cross-linking reactions, allowing shorter processing times. The Young's
modulus of all the composite samples is shown in Fig. 1a. When using
PTSA (sample a) the composite shows higher Young's modulus value,
reaching values around 1.7 GPa, compared with the sample treated in
the same conditions but without using PTSA (sample c). PTSA and high
temperature treatments give the possibility to significantly decrease the
time of process (samples b). Nonetheless, a decrease in the Young's
modulus is observed, probably due to the short time of process. This
might induce lower adhesion between matrix and fibres and lower
stiffness of the humins matrix.
Fig. 1. 1a. Young's modulus of flax fibres composites under different com-
pression moulding conditions a) humins/PTSA resin, 40 min@140 °C; b) hu-
mins/PTSA resin, 20 min@140 °C; c) humins resin, 40 min@140 °C. 1b.
Ultimate tensile stress of flax fibres composites under different compression
moulding conditions a) humins/PTSA resin, 40 min@140 °C; b) humins/PTSA
resin, 20 min@140 °C; c) humins resin, 40 min@140 °C.
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Composites Science and Technology 171 (2019) 70–77
Fig. 1b shows the ultimate tensile strength for all the samples pre-
pared. Ultimate tensile stress is involving the mechanical response at
high deformations, thus it is strongly affected by the adhesion between
fibres and matrix rather than the properties of the matrix itself. The
values of ultimate tensile strength for the two samples treated with the
same conditions (i.e. a and c) is almost the same, being around 15 MPa.
The samples treated for 20 min at 140 °C (i.e. b) shows slightly lower
ultimate tensile strength. As explained before, in this case the interac-
tions between fibres and matrix are less significant, decreasing the
maximum tensile strength value. Similar values of Young's modulus and
tensile strength were found in literature for other all “green” flax fibres
composites [25,61,63]. In particular, the tensile properties obtained in
this work are close to the properties of flax mat composites fabricated
with tannins [52] or tannins/polyfurfuryl alcohol [51] as matrix. Such
comparison with similar reinforcements (i.e. flax mat) underlines the
influence of the matrix. This indicates that humins have matrix prop-
erties similar to tannins. Nonetheless, it is quite difficult to make a fair
comparison with other studies. Many factors can indeed play an im-
portant role on the final properties, such as the structure of the mat, the
optimisation of the resin/fibres ratio and the manufacturing processes
[17,64].
Morphological observations after fracture help to characterize the
interface between the fibres and the matrix. Fig. 2 shows SEM images of
the fracture surface of humins/flax fibres composites (sample a). In
agreement with the good tensile properties, the images reveal a very
good adhesion between humins' matrix and the flax fibres. The matrix is
homogenously embedding the fibres, without any visible gap between
the two phases. No fibre fractions or dislocations is observed, rather the
fracture is coming from the matrix. The same failure profiles have been
previously reported for other flax fibres composites [64].
3.2. Dynamic mechanical analysis
The viscoelastic behaviour of humins/flax composites was studied
by Dynamic Mechanical Analysis (DMA). Fig. 3a shows the variation of
the storage modulus (E′) of the samples as function of temperature.
Small deformations, adjusted initially to be in the linear domain, are
applied on the material. The stress is thus mainly stimulating the matrix
rather than the interface between matrix and fibres since the de-
formation (0.1%) is relatively low to be transferred to the interface.
Thus, the tensile properties highlighted in Fig. 3a are mainly attributed
to the properties of the matrix itself. In all the composite samples, the
storage modulus is observed to decrease with the temperature. In par-
ticular the drop in storage modulus is observed for temperature higher
than the glass transition temperature of the neat matrix (humins),
which can be formally identified by the inflection point of the curve
[65]. The values and the evolution of storage modulus are quite similar
in case of samples a, and c. The properties of the resin for the same
process conditions tend to be quite similar. Sample b shows quite a
different behaviour. The value of storage modulus in the glassy state
(i.e. from −50 °C to 0 °C) is higher compared to the other samples.
However around 25 °C the modulus values of the three samples are in
the same range in agreement with the results from tensile tests (Fig. 1a).
In sample b the humins' resin is less cross-linked as shown by the lower
value of the modulus in the rubbery plateau compared to samples a and
c. The reason is probably due to the different quantity of humins matrix
present in the specimen measured. Indeed heterogeneity in the humins/
flax ratio might occur during the preparation.
The dynamic Tg is the temperature range where a thermosetting
polymer changes from a rigid state to a more flexible or ‘‘rubbery” state.
This temperature could be defined either as the temperature corre-
sponding to the peak maximum of loss modulus (E″) or damping factor
(tan δ) [65]. When studying composites materials, the peak in the E″
curves can be associated with the cooperative α-relaxation (Tα) process
related to the matrix influenced by fibres. In this case, it can be ap-
proximated with the glass transition temperature (Tg) of humins
A. Sangregorio et al.
Fig. 2. SEM pictures of tensile fracture surface of flax/humins composites (image a). High magnification details on the matrix/fibers interface (Images b, c, d).
Fig. 3. 3aStorage modulus and Loss modulus versus temperature of flax fibres
composites under different compression moulding conditions a) humins/PTSA
resin, 40 min@140 °C; b) humins/PTSA resin, 20 min@140 °C; c) humins resin,
40 min@140 °C. 3b. Tan δ versus temperature of flax fibres composites under
different compression moulding conditions a) humins/PTSA resin, 40 min@
140 °C; b) humins/PTSA resin, 20 min@140 °C; c) humins resin, 40 min@
140 °C.
surrounding the fibres. For the samples a, b and c, the Tg (max E″) are
respectively 71 °C, 38 °C and 64 °C. The lower curing time (i.e. 20 min
for sample b) explains the lower degree of cross-link and consequently
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Composites Science and Technology 171 (2019) 70–77
the lower Tg(max E”). The addition of PTSA does not change significantly
the cross-link density and the glass transition of the humins' resin after
40 min of curing as attested by similar relaxation behaviour in sample a
and c.
Relaxation phenomena can be also identified with the variation on
the tan δ curves (Fig. 3 b). Tan δ is the loss factor and represents the
damping within the materials. The peak in tan δ curves is associated
with damping contributions from the matrix and the fibres. The max-
imum of the tan δ peak is similar for sample a and c, i.e., being around
90 °C, in agreement with what was observed for the E″ max values. The
sample treated with PTSA at 140 °C for 20 min (sample b) has a slightly
lower Tg value, i.e. around 80 °C. As explained above, there is a strong
contribution linked to the fibres and their adhesion with matrix,
probably also related to the heterogeneity in the humins/flax ratio.
Similar Tg values were observed in comparable samples prepared with
similar conditions, such as PFA based natural fibres composites [53].
Differences in the amplitude of the tan δ peak are also observed. The
intensity of the tan δ peak gives information on the nature of the in-
terface. The higher is the intensity, the lower is the interface. As the flax
fibres are not relaxing in this temperature region, the changes in the
intensity of the tan delta peak are mostly attributed to modification of
mobility coming from humins chains. Samples a and c show similar
amplitudes of tan δ peak suggesting similar interfaces with the fibres.
The longer processing time thus promotes interactions between matrix
and fibres compared to sample treated for shorter time (i.e. sample b)
which exhibits higher tan δ intensity. This means that interfaces are
poorer in sample b, in agreement with its lower ultimate tensile
strength.
3.3. Thermal stability
The thermal stability of humins/flax fibres composites where mea-
sured by TGA. The thermograms together with the DTG of the mea-
surements under air are shown in Fig. 4 a. The DTG curve of flax fibres
shows three degradation steps. From 40 °C, we observe a weight loss of
about 5% which could be associated to the loss of moisture absorbed by
the hydrophilic fibres. This step is significantly less pronounced in
composites samples (curves a to c), occurring at 100 °C and
A. Sangregorio et al. Composites Science and Technology 171 (2019) 70–77

yield is respectively 25%, 27% and 21% for sample a, b and c. Indeed
the humins alone lead to a relatively high char yield (37%). Presence of
humins in composite decrease the rate of carbonization of flax fibres
and it is particularly highlighted under inert atmosphere.

3.4. Water absorption behaviour and leaching test

One of the biggest concerns while using natural fibres composites is

the possibility to obtain hydrophobic materials. The hydrophilicity of
natural fibres can lead to moisture absorption which can affect the
physical, mechanical and thermal properties. Thus, a very good inter-
action between the two phases can avoid moisture absorption from the
environment. For this purpose, the water absorption behaviour of
composite samples was studied and compared with the behaviour of the
raw flax mat. Composites obtained with and without PTSA catalyst
(respectively sample a and c), processed for 40 min at 140 °C were
chosen as reference samples. The percentage of water gain was calcu-
lated by weight difference of the samples before and after immersion in
water, following the equation:
Wf − Wi
Weight gain % = × 100
Wi (1)

where Wi is the mass of the sample before water immersion and Wf is

the mass after immersion. Fig. 5 shows the water absorption gain as
function of time. The results show that the composites have a very low
moisture uptake compared with the raw flax fibres, quickly reaching
Fig. 4. TGA and DTG measurement under air (a) and under N2 flow (b) of
the saturation point after 1 h and half up to 120 h. This suggests that the
samples prepared under different compression moulding conditions a) humins/
good adhesion between the fibres and the matrix render the final ma-
PTSA resin, 40 min@140 °C; b) humins/PTSA resin, 20 min@140 °C; c) humins
resin, 40 min@140 °C; raw flax fibres mat.
terial more hydrophobic and less prone for water adsorption. This is in
agreement with our previous conclusions obtained from TGA data and
microscopic observations. Indeed, the compact structure at the inter-
corresponding to a loss of mass of around 2.5%. This suggests that the face reduces the void space between the fibres and the matrix through
fibres are well embedded by the matrix and that less free spaces are which water could penetrate.
available. Thus, it is more difficult for fibres to absorb moisture from The leachate waters from the water absorption test were collected
the environment [61,66]. As shown on the DTG curve (Fig. 4a), a and analysed by UPLC. The goal was to verify that a high degree of
second step of weight loss is observed between 200 °C and 400 °C for the crosslinking had been reach and that no more free monomers are
raw fibres, with the peak of maximum rate of weight loss at 330 °C. This leaching out of the samples when let in water. Fig. 6 resume the main
weight loss corresponds to the degradation of hemicellulose around compounds which have been detected and quantified by UPLC.
200–250 °C followed by the degradation of cellulose above 300 °C Fig. 7 highlights the concentration of each compound after in-
[20,67,68]. The results obtained agree with those observed by Wielage creasing leaching time. It should be stressed that most of the leachates
et al. [69]. are released after the first 30 min of leaching. However, the composites
The last step between 400 °C and 550 °C corresponds to the carbo- does not release compounds in water after 1.5 h of leaching while the
nization of the char residue from the flax fibres. In case of humins/flax HMF concentration continue to increase in raw humins even after 48 h.
composites (curve a to c), the degradation peak occurs at slightly lower As shown in Fig. 7 (left), when PTSA is used as catalyst, the con-
temperatures in composites compared to raw fibres, as observed from centration of monomer leaching is significantly lower than for
the DTG in Fig. 4a. This temperatures are lower for samples which have
been subjected to a more pronounced treatment, involving the use of
PTSA (curves a and b). Probably, the use of PTSA increases the ther-
mally unstable non-cellulosic structure in the natural fibres. It is also
interesting to compare the composites samples (curve a to c) with the
humins degradation curve. Humins prepolymerized at 140 °C for 40 min
was chosen as “blank” humins curve, to compare with the composites
containing cross-linked humins. In the blank humins' sample, mass loss
of about 16.5% is observed between 140 °C and 240 °C. This corre-
sponds to loss of volatiles during the degradation/foaming process of
humins at high temperature. This step is about 7.5–8% in the compo-
sites which indeed is in perfect agreement with the 50/50 w/w/hu-
mins/flax fibres ratio.
TGA measurements were done also under N2 flow (Fig. 4b) to check
the variation of the decomposition when inert atmosphere is employed.
The main decomposition peaking around 340 °C is not affected by the
non-oxidative conditions. However, important modification occurs for
the carbonization of the decomposed residues. The flax fibres have a
sufficiently high oxygen content to induce self-carbonization leading to
a char yield of only 3% at 750 °C. At this temperature, the final char Fig. 5. Water absorption gain for raw flax sample and for composites obtained
with humins matrix with and without PTSA.

74
A. Sangregorio et al.
Fig. 6. Main compounds detected in leached water.
Fig. 7. Amount of leached monomers in mg/mL after leaching test in water
from 30 min to 120 h, a) composite flax/humins catalysed by PTSA and com-
posite flax/humins; b) composite flax/humins and humins resin.
composite prepared without catalyst. Leaching water from composites
and from raw humins is compared in Fig. 7 (right). Composites do not
leach any detectable concentration of HMF, while HMFCA can be found
in the water. On the contrary, HMFCA cannot be found when analysing
leached water from raw humins, but HMF can be detected. This sug-
gests that during the curing process of humins in presence of flax fibres,
chemical reactions occurs at the interface between the matrix and the
fibres thus oxidizing the free HMF present in the humins.
4. Conclusion
Humins/flax fibres composites made by compression moulding have
demonstrated a strong potential for the production of all green com-
posites with good tensile properties. Humins interacts with the
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Composites Science and Technology 171 (2019) 70–77
hydrophilic fibres thus creating a good interphase, leading to improved
properties. Tensile properties and DMA of composites showed that rigid
materials with relatively high Tg (> 65 °C) and elastic modulus
(∼1.5 GPa) could be obtained with only cross-linked humins as a ma-
trix. Different compression moulding process conditions were studied.
The importance of the balance between good adhesion and good tensile
properties of the matrix was shown. SEM pictures of the fracture
showed a compact and void free structure at the interphase. Water
absorption stability test revealed much lower water adsorption com-
pared to raw mat. The leachates were identified and mainly HMFCA
was detected as the results of potential oxidation of HMF in presence of
fibres. The study demonstrated that humins can be valorised as ther-
moset resin for the production of natural fibres composites, obtaining
good tensile and water resistance properties. These composites could be
employed in large scale for automotive application or for building
materials.
Declarations of interest
None.
Acknowledgment
The authors acknowledge the EU framework Program Horizon 2020
for financial support as in the HUGS project (ID: 675325). The authors
would also like to thank Synvina C.V. for providing humins samples and
for scientific and technical support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.compscitech.2018.12.008.
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