Construction and Building Materials 139 (2017) 594601

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Construction and Building Materials

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

Virtual Special Issue

Bio Based Building Materials
Humins as promising material for producing sustainable
carbohydrate-derived building materials
Alice Mija a,, Jan C. van der Waal b, Jean-Mathieu Pin a, Nathanael Guigo a, Ed de Jong b,
a
Universit Cte dAzur, CNRS, Laboratoire de Physique de la Matire Condense LPMC UMR 7336, Parc Valrose, 06100 Nice, France
b
Avantium Chemicals B.V., Zekeringstraat 29, 1014 BV Amsterdam, The Netherlands

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Humins are original unique

macromolecules, sub-products during
polysaccharide conversion.
 Furfuryl alcohol/humins resins with
good viscosity, stability and curing
behaviour were prepared.
 New thermosetting materials suitable
for applications in a.o. building
products were produced.

a r t i c l e i n f o a b s t r a c t

Article history: Nowadays biobased building materials are used in various fields and for a wide range of applications such
Received 6 July 2016 as polymers, fillers, coatings, adhesives, impregnation materials or high performance composites. This
Received in revised form 2 November 2016 work focuses on humins, a biomacromolecular by-product of a HydroxyMethylFurfural/FuranDiCarbox
Accepted 4 November 2016
ylic Acid biorefinery. Humins are obtained by acidic treatment of polysaccharides and show very inter-
Available online 9 November 2016
esting potential as a reactive, semi-ductile thermoset matrix to impregnate cellulosic fibres. Therefore,
humins have the essential characteristics to develop a new class of thermoset materials and composites,
Keywords:
offering excellent possibilities to increase the renewable carbon content of the final products and
Biorefinery
Polysaccharide
improve its properties. A proper characterization of the neat humins in terms of solubility, flow behaviour
Humins and thermal resistance is essential in order to find the optimal parameters of processing humins solutions
Thermosets as well as co-reactive mixtures for impregnations or to prepare composites. In addition the study further
Composites indicates that humins enhance the modulus and the tensile strength of pure polyfurfurylalcohol resins. It
Hydroxymethylfurfural (HMF) was also shown that there is a difference in behaviour when sulfuric acid or maleic anhydride is used as
FuranDiCarboxylic Acid (FDCA) initiator. The most optimal initiator will depend on application and preferred processing conditions.
These encouraging results assure an important future for humins as economic green matrix for the pro-
duction of composites and wood impregnation.
2016 Elsevier Ltd. All rights reserved.

1. Introduction
Corresponding authors.
E-mail addresses: Alice.MIJA@unice.fr (A. Mija), ed.deJong@avantium.com One of the current efforts of both academic and industrial
(E. de Jong). research focuses on the use of biomass as a renewable source for

http://dx.doi.org/10.1016/j.conbuildmat.2016.11.019
0950-0618/ 2016 Elsevier Ltd. All rights reserved.
 A. Mija et al. / Construction and Building Materials 139 (2017) 594601
platform molecules. The major challenge is to find adequate sus-
tainable alternative resources to fossil feedstocks. In this regard,
also lignocellulosic biomass, i.e. the non-edible part of plants, can
be an important source of fuels and chemicals. As an example,
starting from (hemi-)celluloses, biorefineries can produce furan
derivatives and levulinic acid (LA) which are positioned in the
top 12 of value added molecules from carbohydrates [18].
The growing interest to develop sustainable biomass conver-
sion processes at large scale has been exemplified by the SME
Avantium, a CleanTech top 100 company (http://www.clean-
tech.com/indexes/global-cleantech-100/). Avantium has devel-
oped the YXY Technology. The YXY technology platform
produces a wide range of novel materials and products, all 100%
biobased, by converting plant-based sugars into chemical building
blocks, like Furanics and Levulinics, for plastics and other applica-
tions. YXY is a game-changing technology that offers biobased
products and fuels with superior properties at market competitive
prices [19]. The basic philosophy behind Avantiums YXY technol-
ogy is to develop products from renewable sources that compete
on price and performance and with a superior environmental
footprint. A pilot plant is operating on a 24/7 basis since 2011
to convert carbohydrates into Alkoxymethylfurfural (RMF) com-
pounds, further processed to a new class of furanic building
blocks based on FuranDiCarboxylic Acid (FDCA) denoted as YXY
[9,10]. FDCA resembles the bulk chemical terephthalic acid and
can be used as building blocks of polymers such as polyesters,
polyamides and polyurethanes. It was shown that producing the
polyester PEF, using FDCA and mono-ethylene glycol, polymers
can be produced with strongly improved properties compared
to PET [1012].
Moreover, biorefineries will be challenged to valorise the
by-products accompanying glucose or fructose conversion into
these molecules. For example, the synthesis of 5-hydroxymethyl-
furfural (HMF), 5-alkoxymethylfurfural and levulinic acid (LA) by
acid catalyzed fructose dehydration, is complemented with the for-
mation of substantial quantities of a black tarry by-product, a com-
plex polyfuranic polymer, called humins [6,7,1318]. In the case of
the YXY process two main classes of side compounds are produced:
humins and levulinic acid/alkyl levulinates [19,25]. Recently, the
establishment of the company Synvina, a joint venture between
Avantium and BASF was announced, its main target the building
of the first commercial scale FDCA plant as well as launching FDCA
and PEF to the market. This plant of around 2550 ktonnes/year
FDCA output will also produce 10s of ktonnes of humins.
Despite humins are known for almost a century [20,21], and as
product resulting from prolonged sugar degradation reactions in
the caramelisation process, its main application is still limited
to energy and heat applications such as burning and gasification
[13]. Its valorisation into higher added-value applications will
be key for making biomass conversion processes economically
feasible many. Recently we showed with initial work that humins
can be successfully used as a matrix to produce composites
[18,22]. The polyfuranic structure of humins and its high func-
tionality are important structural factors that should be consid-
ered and even exploited in order to develop interesting
biobased thermosets materials or as a matrix for impregnations
and composites.
Humins are heterogeneous amorphous biomacromolecules,
considered to have the idealized morphology of spherical core-
shell architecture [22]. The chemical structure of humins consists
of furfural and hydroxymethylfurfural moieties also with carbohy-
drate, levulinate and alkoxymethylfurfural chains linked together
into macromolecules by ether, acetal bonds or aliphatic linkages.
The nature of terminal groups could be of carboxylic, ketone, alde-
hyde and/or hydroxyl nature. Also the presence of certain solvents
such as acids or alcohols during the carbohydrate dehydration
595
reactions could instigate the appearance of other functional groups
such as alkoxy and ester groups [4,5,15,16,23,24].
The mechanism of the humins formation is supposed to be an
acid catalyzed condensation between its intermediates formed
and possibly also with the starting carbohydrate during their
transformation to HMF/MMF/LA, leading to a network of furan
rings. A model structure by furan rings connected via alkylene moi-
eties is proposed by van Zandvoort et al. [1517] and schematized
here on Fig. 1.
In the present work, humins from Avantiums biorefinery
derived from acid-catalyzed dehydration of fructose in methanol
produced in YXYs pilot plant were studied as resin components.
Understanding the nature and the properties of humins is one of
the objectives to evaluate its application potential. Various investi-
gations were employed to gain more knowledge on its behaviour
and reactivity. Solubility tests, Fourier Transform-InfraRed (FT-IR)
spectroscopy, UV spectroscopy, Nuclear Magnetic Resonance
(NMR) spectroscopy, Differential Scanning Calorimetry (DSC) and
ThermoGravimetric Analysis (TGA) have proven to be very useful
to show the capacity of humins to auto-crosslink, or to lead to
resins or composites after various chemical modifications to resins
or foams.
The influence of humins structure and chemical compositions
on chemical reactivity has shown that this material is very ver-
satile, permitting the development of thermosets with very
promising properties for impregnation of wood, natural fibres
or paper. Comparative studies with other furanic thermosets
demonstrate that superior properties have been achieved com-
pared to polyfurfuryl alcohol (PFA) and PFA/lignin composites
[1822].
The temperature of resin curing is a key issue for a successful
industrial introduction. It was shown that using co-catalysis with
a strong acid can reduce the temperature of curing. This investi-
gation is particularly useful for the 2 steps resin curing strat-
egy. Indeed, after the first introduction of 1/2 the amount of
catalyst and the pre-heating, the resin was cooled down and
then a second batch of the same or different co-catalyst was
added at room temperature. The present work highlights the
crucial role of resin composition, time and temperature on struc-
tural and morphological changes of resins and properties of
obtained composites.
2. Experimental section
2.1. Materials
Furfuryl alcohol (FA) (purity: P98%), sulfuric acid (purity:
P96%), maleic anhydride (MA) (purity: P99%), isopropyl alcohol
(IPA), acetic acid (AcOH), methyl levulinate (ML), diethyl ether
(DEE), acetonitrile (AN), acetone (AcO), and methanol (MeOH) all
analytical reagents were purchased from Sigma-Aldrich and were
used as received.
Humins were produced by Avantium Chemicals at their Pilot
Plant in Geleen, The Netherlands, by acidic conversion of fructose
in methanol solvent. These humins were distilled under high vac-
uum to reach low 5-hydroxymethylfurfural (HMF) and 5-
methoxymethylfurfural (MMF) content (<5% by weight). The
humins composition obtained by elemental analysis (ICP) is
approximately 60 wt.% C, 32 wt.% O, and 5 wt.% H. Their heating
value is around 23 MJ/kg. Humins have the appearance of very vis-
cous, shiny, black bitumen. Humins complex viscosities at 60 C
are around 69254 Pa.s, depending on the batch composition.
These values were determined in accordance with ASTM D7175
using an Anton Paar MCR 102 rheometer at 10 Hz.
Cellulose composites were made with Whatman 40 filter paper
having a diameter of 110 mm and a weight of 900 mg.
596 A. Mija et al. / Construction and Building Materials 139 (2017) 594601
Fig. 1. Bio-derived platform and humins as condensation by-product.
2.2. Resins preparation
The reference resin is based on PFA and consisted of 95% of FA
and 5% of acid catalyst (MA) on weight basis. This quantity of cat-
alyst was chosen as the optimal concentration, considering that
humins will interact with the acidic catalyst and thus decrease
the intrinsic FA reactivity.
To prepare PFA/Humins thermoset resin a 40/55/5 (w/w) FA/
Humin/MA ratio was used, with 5% being the initiator part. Preced-
ing the addition of the acidic initiator, the FA was mixed with
humins at 105 C for 20 min under mechanical stirring until a
homogeneous, viscous, black liquid was formed. Then, the maleic
anhydride (5% w/w) was introduced in two equal steps of 2.5%
w/w. On the basis of DSC investigations (not shown here), intro-
duction of viscous condensed humins into the system decreases
the overall reactivity and shifts the polycondensation peak to a
higher temperature compared to those of the pure FA/MA mix-
tures. After cooling to 80 C, the last addition of 2.5% w/w initiator
was done. Subsequently, the mixture was stirred for another 5 min
and cooled to room temperature.
In parallel, sulfuric acid was tested as a co-catalyst. The quantity
of sulfuric acid was fixed for this first experiment to 1 % (w/w) of
pure acid (96%) diluted in an aqueous solution of 20 % by weight.
The quantity of sulfuric acid should be further tailored in function
of the reached curing temperature.
A homogeneous, viscous, shiny, black resin was obtained in
each case. The resins were stored in the fridge, and no phase sep-
aration was observed, even after several weeks.
The different cellulose composites were processed by impreg-
nation of the above-mentioned resins with cellulose filter. After
impregnation of the filter at room temperature, the system was
pressed and put in an oven for final curing at 160 C during 3 h.
After curing, the final cellulose/resin ratio was about 1/1.
2.3. Experimental techniques
Solubility tests were done using Technobis Crystallization Sys-
tems Crystal16 multiple-reactor system which is a very useful
tool to determine solubility curves. The solubilities of 0.3% solu-
tions of humins in following solvents were tested: isopropyl alco-
hol (IPA), acetic acid (AcOH), methyl levulinate (ML), diethyl ether
(DEE), acetonitrile (AN), acetone (AcO), water, and methanol
(MeOH) were studied. The experimental reactors at a volume of
1 mL, equipped with Teflon mini agitators, followed the controlled
temperature program via aluminium reactor blocks encased in a
robust bench top. These blocks are electrically heated and cooled
by a combination of Peltier elements and a heater. Two heating-
cooling cycles from 25 to 90 C at 10 C.min 1 were applied and
the quantification of solubility was done by turbidity measure-
ment, in transmission mode.
Infrared Spectroscopy. A PerkinElmer Spectrum BX II spec-
trophotometer was used in attenuated total reflectance (ATR)
mode with a diamond crystal. The spectrum of air was recorded
as background. A total of 1000 scans with a resolution of 1 cm 1
was recorded for each sample to obtain sufficient sensitivity.
Thermogravimetric analysis (TGA)
Thermogravimetric measurements were carried out on a TGA
851e from Mettler-Toledo. The microbalance has a precision of
0.1 lg. Samples of about 10 mg were placed into 70 lL alumina
pans. The samples were heated at 10 C min 1 from 25 C to
 A. Mija et al. / Construction and Building Materials 139 (2017) 594601 597

1000 C under air and nitrogen gas flow of 50 mL.min 1

to deter-
mine their thermal stability.
Tensile tests
The stress-strain curves were recorded on an Instron 5565
apparatus in tensile mode with crosshead speed of 2 mm min 1.
After curing, the samples were cut into strips of around
100  10  0.25 (length  width  thickness) mm. The length
between the clamps was fixed to 40 mm. For each composite, the
average values and standard deviations of Youngs modulus and
tensile strength were calculated from seven measurements.
Rheometry
Rheological behaviour of humins was followed using an Anton
Paar rheometer. The measurements were operated on plate-plate
geometries (25 mm diameter and 1 mm gap) with strain convec-
tion heating. Because the humins are difficult to be studied under
shear conditions we used oscillatory measurements. This method
gives access to the complex viscosity as function of angular fre-
quency. Complex viscosity, (g(x)) (Pa.s) is obtained by dividing
the measured complex modulus by the angular frequency. The
obtained data can subsequently be correlated to shear viscosity
as function of the shear rate. To study the influence of the temper-
ature, the tests were carried out in isothermal programs at 40, 80
and 100 C in angular frequency mode (varying from 0.1 to
100 Hz), 2% amplitude, with oscillation.
in various solvents was determined using Crystal16 analytical
method (Table 1 and Fig. 2).
As example in hot water only a small fraction, around 5%, of
humins gave an approximately homogenous solution; in presence
of acetone it seems that an extraction of lower molecular weight
polymers occurs. Among the eight chosen solvents only three
showed good humins dissolution. This can be seen in Fig. 2 by
the visual aspect of the solutions and in Fig. 3 by the measured
transmission. The methyl levulinate give a clear homogeneous
solution with 100% of transmission, the acetic acid increases its
solubility at T > 35 C reaching a transmission of 80%, and the
methanol has a transmission of 70% (Figs. 2 and 3). IPA solvent
arrives to extract some humins fractions at a temperature above
55 C (Fig. 3), the photo of Fig. 2b shows some undissolved residue.
In contrast, in DEE the humins are insoluble, though a yellowish
fraction is extracted.
These results are in agreement with the mixed of non-polar and
polar functional groups present on the surface of humins. Solvents
that are organic and can form a strong interaction with the polar
groups, will be favoured. Alcohol and carboxylic acids that can
form H-bridges have the highest solubility power. However, water,
which can form H-bridges, does not have enough interaction with
the non-polar CH and C = C groups, whereas acetone and diethyl
ether do not have a sufficiently strong polar interaction through
the ketone or ether group, respectively.
Solubility determined using Crystal16 with a heating/cooling
rate of 10 C.min 1 Solubility of humins macrostructures as deter-
mined by changes in turbidity of the liquid phase due to dispersion
of humins spheres.

3. Results and discussion

3.1. Neat humins DEE IPA

100
ML
3.1.1. Solubility
Humins being generated by condensation of intermediates 80 AcOH
Transmission / %

formed during dehydration of carbohydrates is a solid macro-

MeOH
molecular material with heterogeneous aromatic structure and 60
very limited solubility in common solvents. Solubility of humins

40
H2 O
Table 1
Humins solutions for solubility studies.
20
No Humins (mg) Solvent (1 mL) AN
1 2.2 IPA
0 AcO
2 2.2 AcOH
3 1.8 ML
4 1.8 DEE 30 40 50 60 70 80 90
5 1.7 AN
6 2.9 AcO
Temperature / C
7 1.4 H2O
8 1.8 MeOH Fig. 3. Solubility as function of temperature for humins solutions at 2090 C
second heating.

1
Fig. 2. Humins solutions in different solvents numbered 18 from left to right for explanation) before (a) and after two 2090 C heating-cooling cycles at 10 C.min .
598 A. Mija et al. / Construction and Building Materials 139 (2017) 594601
3.1.2. Rheological behaviour
The rheological behaviour of humins was tested in isothermal
conditions. First, the temperature of 40 C was chosen to follow
the flow behaviour of humins at temperature of processing. Then,
higher temperatures, of 80 and 100 C were applied as limit of tem-
perature of utilization, due to chemical changes occurring as pre-
sented in TGA studies. Fig. 4 compares the effect of temperature
on the complex viscosity and its evolution with angular frequency.
Obviously, the complex viscosity decreases drastically with tem-
perature, with 2 decades from 1200 Pa.s at 40 C to 10 Pa.s at
80 C.
At 40 C we can observe that the viscosity is not constant but
decreases with the shear rate which is the sign of a shear thin-
ning or pseudoplastic behaviour. This non-Newtonian behaviour
is of practical importance in the processing of humins. A
decreased viscosity can facilitate material process and is associ-
ated with the development of polymer elasticity. This elasticity
could be correlated with some molecular orientation, probably
due to structural characteristics of humins. The bulk of the
humins consist of spheres and from our solubility and IR study,
it was concluded that a significant of polar CO and C = O groups
must be present of the surface. At low temperatures these groups
can contribute to weak interaction between spheres through
hydrogen bonds entanglements, etc, depending on shear rate, giv-
ing non-Newtonian viscosity at 40 C. At 80 C and 100 C, this
sphere-sphere interaction is reduced due to the increase mobility
of the individual spheres, and the humins behaviour suggest an
almost constant viscosity until high value of frequency. At
100 C some irregularities appears on the curves which might
be associated with volatilization of by-products at such high tem-
perature or further condensation of humins spheres to larger
agglomerates. Future works should elucidate the influence of
the key parameters such as the composition and thermal history
of humins on this behavior.
FS
10 4
40 C
Pas
3
10
2
10
| *|
80 C
10
1 the feature at 1665 cm 1 could arise from the C@O stretch of the
100 C
10 0
1 10 100
Angular Frequency
Anton Paar GmbH
Fig. 4. Humins evolution of complex viscosity (g ) in function of angular frequency
(x) at 40, 80 and 100 C.
3.1.3. Thermal stability
Thermogravimetric analyses of humins were performed in both,
nitrogen and air environments where the reaction medium favours
the pyrolysis or the thermo-oxidative degradation process. The
thermal decomposition temperature corresponding to 10% of
weight loss (Td90% on Fig. 5) is 170 C.
As seen in Fig. 5 the derivative plots of weight loss curve (DTG)
show evidence of several steps of degradation and the comparison
of thermal degradation of humins in inert and reactive environ-
ments shows a significant difference with the reaction medium
only in the second part of degradation, i.e. at T > 480 C.
Based on the major DTG curves, the decomposition patterns
under N2 could be divided into 2 regions and that under air into
3 regions. The first region is almost identical for both media denot-
ing a primary devolatilization and structural changes in the tem-
perature range from 120 to 270 C. During this step the sample
lost around 29.41% of weight.
Under nitrogen, the second step of degradation occurs in 300
600 C temperature range. In these two steps of degradation,
humins undergo dehydration, decarboxylation, decarbonylation
together with the decomposition of the network structure. Some
condensations/recombinations of formed fragments are possible,
the final char yield being around 38%.
Under oxidative medium the second and the third decomposi-
tion steps appear as peaks in DTG curve at about 300400 C and
420720 C respectively. In the last temperature range the humins
thermo-oxidative degradation is very significant, the final residue
being around 4.15%.
In conclusion, humins are very sensitive to thermal treatment.
This results in thermal degradation involving complex chemical,
thermolysis and/or thermo-oxidative mechanisms. To obtain a sce-
nario of thermal scissions of networks, a deeper study of mecha-
nism of degradation is needed.
The data presented above show that humins are potentially
usable as a resin component for composite manufacturing. The
next session will discuss the effects of humins incorporation in a
PFA resin on tensile strength as well as Youngs modulus. In addi-
tion the different behaviour of sulfuric acid compared to MA as a
resinification initiator will be presented and discussed.
3.2. PFA/humins thermosets and composites
3.2.1. FT-IR analysis of humins and PFA/humins thermoset resins
The fructose-based humins spectrum is shown in Fig. 6. The
molecular structure of humins is mainly derived from HMF and
5-methoxymethylfurfural (MMF). The peak at 1515 cm-1 is
assigned to Carbon-Carbon (C@C) stretching in furan rings while
the peak at 1020 corresponds to Carbon-Oxygen (CO) stretching.
In the same case as PFA, the composite peaks between 800 and
750 cm 1 are attributed to the out of plan Carbon-Hydrogen (C
H) bending of the different substituted furans. According to Patil
et al. [6] the peak at 1712 cm 1 together with the peak around
1600 cm 1 in humins are characteristic of carbonyl group conju-
gated to an alkene group. Finally, it should be mentioned that
MMF and HMFs aldehyde group.
The spectrum of the pre-polymerized 40/55H/5 resin corre-
sponds approximately to the superposition of the signals from
the PFA resin and those from the humins. Some features can be
attributed to specific interactions between the PFA network and
the humins. A new band develops at 868 cm 1 which is neither vis-
1/s 1,000 ible in the spectrum of PFA resin or in the spectrum of humins. The
peaks appearing within this wave number region are generally
attributed either to CH wagging of methylene linkages or CO
stretching from Diels-Alder cyclo adducts. This might indicate that
novel kinds of interactions were created between the side chain
 A. Mija et al. / Construction and Building Materials 139 (2017) 594601 599

Fig. 5. Thermogravimetric analysis of humins under air (black) and under N2 (red) systems at 10 C.min 1 relative weight loss (upper part of the Figure) and derivative weight
loss (lower part). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

humins
Transmission a.u.

resin 40/55H/5

1735 1714 868 798 738

1800 1600 1400 1200 1000 800 600

Wavenumber / cm-1
Fig. 6. IR spectra of humins (black) and 40/55H/5 cured resins (red). (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
oxygen groups of the humins and the furanic rings from the PFA.
Moreover, clear-cut shoulders appear at 1714 and 1735 cm 1 in
the carbonyl stretching region. The chemical environment of the
carbonyl groups present in the aliphatic parts of the humins has
been modified probably due to new interactions with the polyfur-
furyl alcohol network. It should also be mentioned that the CH
out of plane bending of the furan rings appears at 798 and
738 cm 1 for the 40/55H/5 resin. These peaks are broader and
slightly shifted to higher wavenumbers compared to the PFA resin.
It denotes a more complex network of furan rings due to intercon-
nections between the two systems.
Fig. 7. Impregnation tests on textile fibres and wood (Wood veneer on the left is
untreated Birch wood).
3.2.2. Mechanical properties of PFA/humins composites
Different fibre and lignocellulosic matrices were impregnated
by the humins resins resulting in very appealing composites
(Fig. 7). To asses physical characteristics, the final Whatman com-
posites after impregnation and curing at 160 C were compared to
the pure PFA as reference (Fig. 8). The composite with the sulfuric
acid initiated resin (40/55H/2.5/1) shows lower tensile strength
values than the MA initiated humins resin but both are signifi-
cantly better than the results achieved with pure PFA (95/0/5)resin.
The Young modulus of the sulfuric acid initiated resin
(40/55H/2.5/1) is very close to the 40/55H/5 composite which
demonstrates the importance of the first pre-curing stage with
the 2.5% of MA (Fig. 8a). However, the final result is better than
600 A. Mija et al. / Construction and Building Materials 139 (2017) 594601
4
(a)
Young's modulus / GPa
3
2 15
1
0 0
95/0/5 40/55H/2.5/1 (H2SO4)
Fig. 8. Influence of sulfuric acid as co-catalyst for resin curing on Youngs modulus (a) and tensile strength (b).
for biocomposites processed with pure PFA, and thus showing good
omen for several applications. Furthermore, some qualitative tests
with a higher content of sulfuric acid have been performed and
reveal a good potential of curing for these kinds of resins, at room
temperature.
4. Conclusions
This work shows that humins as by-products from bioprocess-
ing have the essential characteristics to develop a new class of
thermoset materials and composites, offering excellent possibili-
ties to increase the renewable carbon content of the final products.
In the first part, we have shown that the proper characterization of
the neat humins in terms of solubility, flow behaviour and thermal
resistance is essential in order to find the optimal parameters of
processing humins solutions as well as co-reactive mixtures for
impregnations or to prepare composites. In the second part, the
work gives a short view on the obtained chemical structures after
co-reacting with furanic PFA. Earlier work by Pin et al. [17] had
shown that there is a strong interfacial adhesion between cellulosic
fibres and humins resins. This study further indicates that humins
enhance the modulus and the tensile strength of pure PFA resins by
improving the interfacial adhesion between cellulose and polyfur-
furyl alcohol based resins independently of the initiator used. It
was also shown that there is a difference in behaviour when sulfu-
ric acid or MA is used as initiator. The most optimal initiator will
depend on application and preferred processing conditions. Fur-
ther research should also evaluate the effects of having HMF
derived polymers instead of FA derived polymers has an effect on
the strength properties of the resulting resins. However, it can
already be concluded that incorporating large amounts of humins
in PFA resins together with cellulosic fibres/matrix result in bio-
composites having great potential for building applications such
as plywood, boards, flooring, decking, etc. because besides the
technological advantages also the cost price of humins is substan-
tially lower compared with furfuryl alcohol.
Acknowledgments
The authors acknowledge the European Commission for finan-
cial support: BIOFUR FP7-PEOPLE-2012-IAPP project BIOpolymers
and BIOfuels from FURan based building blocks.
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