polymers

Review
Sustainable Alternatives for the Development of Thermoset
Composites with Low Environmental Impact
Patricia Ares-Elejoste 1 , Ruben Seoane-Rivero 1 , Iñaki Gandarias 2 , Aitziber Iturmendi 1 and Koldo Gondra 1, *

1 GAIKER Technology Centre, Basque Research and Technology Alliance (BRTA), Parque Tecnológico de
Bizkaia, Edificio 202, 48170 Zamudio, Spain; [email protected] (P.A.-E.); [email protected] (R.S.-R.)
2 Chemical and Environmental Engineering Department, University of the Basque Country (UPV/EHU),
Alameda Urquijo s/n, 48013 Bilbao, Spain
* Correspondence: [email protected]

Abstract: The current concerns of both society and the materials industries about the environmental
impact of thermoset composites, as well as new legislation, have led the scientific sector to search for
more sustainable alternatives to reduce the environmental impact of thermoset composites. Until
now, to a large extent, sustainable reinforcements have been used to manufacture more sustainable
composites and thus contribute to the reduction of pollutants. However, in recent years, new
alternatives have been developed, such as thermosetting resins with bio-based content and/or
systems such as recyclable amines and vitrimers that enable recycling/reuse. Throughout this
review, some new bio-based thermoset systems as well as new recyclable systems and sustainable
reinforcements are described, and a brief overview of the biocomposites market and its impact is
shown. By way of conclusion, it should be noted that although significant improvements have been
achieved, other alternatives ought to be researched.

Keywords: sustainability; thermoset composites; bio-based; sustainable reinforcements; biocomposites

applications

Citation: Ares-Elejoste, P.;

Seoane-Rivero, R.; Gandarias, I.;
1. Introduction
Iturmendi, A.; Gondra, K. Sustainable One of the most pressing problems in the 21st century is the continuing depletion
Alternatives for the Development of of crude oil, i.e., the scarcity of petroleum-based products, and serious environmental
Thermoset Composites with Low problems such as pollution. This is why, for materials such as composites, increasing
Environmental Impact. Polymers 2023, emphasis is being placed on research for renewable alternatives [1–4].
15, 2939. https://doi.org/10.3390/ Thermosetting materials are mostly affected by this point, as they have the disad-
polym15132939 vantage of not being recyclable, which translates into an increase in waste landfills [1].
Academic Editor: Beom Soo Kim However, in recent years, thermosetting resins have been developed using renewable
sources, which, despite not being recyclable, represent a significant improvement in terms
Received: 16 May 2023 of sustainability. On the other hand, in addition to these bio-based resins, the research
Revised: 13 June 2023
sector has developed alternatives for the recycling of thermosets and vitrimers, which
Accepted: 30 June 2023
allows composites to be remolded using a heat source once cured.
Published: 4 July 2023
In order to make these materials more sustainable, the use of more renewable rein-
forcements such as cores and natural fibers, which are used in various manufacturing
processes to obtain products such as clothing, sports equipment, etc., has been increasing
Copyright: © 2023 by the authors.
for several years [5–8], resulting in a production of approximately 30,000,000 tons/year.
Licensee MDPI, Basel, Switzerland. It should be noted that, in addition to the fact that these types of reinforcements have
This article is an open access article an excellent specific modulus and elongation at break, they contribute to improving the
distributed under the terms and economic situation of farmers, as these fibers come from lignocellulosic products.
conditions of the Creative Commons Throughout this review, several issues, such as bio-based resins (epoxy, benzoxazine,
Attribution (CC BY) license (https:// polyesther, etc.), sustainable reinforcements (cores, foams, natural fibers, etc.), recyclable
creativecommons.org/licenses/by/ routes for thermoset composites, and a brief analysis of the bio-based composites market,
4.0/). will be discussed.

Polymers 2023, 15, 2939. https://doi.org/10.3390/polym15132939 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 2939 2 of 16

2. Sustainable Thermoset Resins

The high interest in the development of sustainable thermosetting resins is mainly due
to their high properties. Thanks to their ability to form crosslinked networks after curing,
these resins present excellent chemical properties, good thermal and mechanical properties,
and excellent stability [2]. Within this group of resins, the following could be found:
epoxy resins, polyester, vinylester, and benzoxazine (phenolic). Nevertheless, to synthesize
bio-based thermosetting resins, it should be taken into account that, due to the complex
structures of biomass resources, it is not practical or efficient to use them directly. Thus,
biomass needs to be transformed into more useful or simpler molecules called building
blocks or intermediates [9]. In addition, among the possible sustainable alternatives, there
are also furan resins, which can be obtained from agricultural by-products.
The following is a summary of the sustainable resins currently available on the market
and the renewable sources from which they are derived. These have been developed
through the exploitation of renewable feedstock, formula optimization, copolymeriza-
tion, etc.

2.1. Furan Resin

As mentioned above, furan resin is obtained from agricultural by-products [10]. In
particular, furfural is obtained from furan by catalytic hydrolysis of biomass. This is then
transformed into furfuryl alcohol, and through condensation reactions and a Diels–Alder
cycloaddition, furan resin is obtained.
The main advantage of this type of resin is that it is a good substitute for phenolic
resins, which are in demand because of their good thermal stability, mechanical properties,
and durability.
Table 1 below summarizes the advantages and disadvantages of these resins.

Table 1. Advantages and disadvantages of furan resins.

Advantages Disadvantages
Derived from renewable resources High variation of viscosity with temperature
Good chemical and thermal resistance High shrinkage during curing
Free monomer content: ≥1% H2 O generation during polymerization
Good fire properties
Similar performance to phenolic resins

As mentioned above, the thermal stability of these resins is one of the most important
factors. In fact, according to the research carried out by [11], this kind of resin could be
used in the manufacturing of materials for the railway sector. Additionally, they are used
in the foundry industry as sand binders for the manufacture of molds.

2.2. Bio-Based Benzoxazine Resin

Benzoxazine resin (Figure 1) is a type of thermosetting phenolic resin that has been
gaining interest in recent years due to its many advantages, including low water absorption,
good thermal stability, zero shrinkage, a high char yield, and no by-products during the
curing reaction [2]. In terms of sustainability, these resins are good candidates, as they
are flexible in their molecular design, which allows their synthesis using several types of
phenols and amines, the components of which can be obtained from natural sources. In
fact, thanks to the wide variety of sources from which these products can be obtained, it is
possible to synthesize benzoxazine resins with properties even superior to those obtained
from petroleum.
In fact, if a comparison is made between amines and phenols, in nature it is more
common to find different types of phenols of biological origin that contain different sub-
stituents that allow the development of polybenzoxazine materials with different properties
and characteristics.
 resins are good candidates, as they are flexible in their molecular design, which
their synthesis using several types of phenols and amines, the components of w
be obtained from natural sources. In fact, thanks to the wide variety of sources from
Polymers 2023, 15, 2939 these products can be obtained, it is possible to synthesize benzoxazine 3 of resins
16 wi
erties even superior to those obtained from petroleum.

Figure
Figure 1. 1. Benzoxazine
Benzoxazine structure.
structure.

One of the main natural sources of aromatic substances is lignin, from which com-
poundsInsuch
fact,
as if a comparison
vanillin, eugenol, andis guaiacol
made between amines
can be obtained and and
used phenols, in nature it
for the synthesis
common
of to find different types of phenols of biological origin that contain differ
benzoxazine.
stituents that allow the
Some characteristics development
of these compoundsof arepolybenzoxazine
shown below: materials with different
•tiesGuaiacol:
and characteristics.
a compound with a simple structure for which a copolymerization reaction
isOne
necessary
of thein order
maintonatural
obtain better performance.
sources of aromatic substances is lignin, from whi
• Vanillin: a compound whose aldehyde group could remain intact during the synthesis
pounds such as vanillin,
of the benzoxazine monomers.
eugenol, and guaiacol can be obtained and used for the s
•of benzoxazine.
Eugenol: it has both an allyl group and a phenolic hydroxyl group, which is how
Some characteristics
bio-based bisphenol can beof these compounds are shown below:
obtained.
• InGuaiacol:
addition toa the compounds
compound aforementioned,
with these types
a simple structure of resins
for which can also be
a copolymerization
obtained from coumarin, sesamol, and arbutin.
is necessary in order to obtain better performance.
With regard to the amines that can be used in development, the most widely used is
• Vanillin:asaitcompound
furfurylamine, improves thewhose
hydrogenaldehyde
bondinggroup
system.could remainitintact
Nevertheless, shouldduring
be the
sis of the benzoxazine monomers.
noted that compared to phenols, there are not as many sustainable varieties, which makes
it•difficult to obtain
Eugenol: it resins
has both withan
different properties.
allyl group and a phenolic hydroxyl group, which is h
Finally, other lignin-derived acids can also be used, such as ferulic acid, phloretic acid,
based bisphenol can be obtained.
and p-coumaric acid, whose carboxylic acid groups can lower the benzoxazine ring-opening
In addition
temperature to around to 130
the◦ C.
compounds aforementioned, these types of resins can als
tained from coumarin, sesamol, and arbutin.
2.3. Bio-Based Epoxy Resin
With regard to the amines that can be used in development, the most widely
Among the bio-based resins, epoxy resins are currently the most developed. These
furfurylamine, as it improves the hydrogen bonding system. Nevertheless, it sh
resins have great advantages such as low shrinkage, easy moldability, good adhesion,
noted
and highthat compared
resistance to phenols,
to weathering, there
which makesarethem
not as many
very sustainable
attractive varieties, whic
for the numerous
it difficult in
applications tovarious
obtainsectors.
resins Most
withofdifferent properties.
these resins (nearly 90%) are developed through
the useFinally,
of epichlorohydrin
other lignin-derived acids canpresence
and bisphenol A (in the also beofused,
sodium hydroxide),
such the acid, p
as ferulic
latter being a compound that is considerably harmful to both health and the environment.
acid, and p-coumaric acid, whose carboxylic acid groups can lower the benzoxaz
For this reason, one of the key objectives has been the synthesis of these resins from
opening temperature
natural elements. to aroundof130
The methodology °C.
the preparation of epoxy resins means that com-
pounds of related renewable origin (Figure 2) have great potential for the synthesis of
2.3. Bio-Based
epoxy Epoxy
resins, which Resininto a wide range of possibilities for obtaining this type of
translates
resin with bio-based content. Furthermore, it should be taken into account that, during the
Among the bio-based resins, epoxy resins are currently the most develope
curing reaction, the epoxy group could be ring-opened by carboxyl, anhydride, or amine.
Itresins havepossible
is therefore great advantages such assystems
to design bio-based low shrinkage, easyof
using a mixture moldability, good adhes
several renewable
high resistance
curing to weathering,
agents. To obtain which
bio-based epoxy makes
resins, therethem very
are two attractive
types of routes:for
(i) the numerou
direct
reaction
cationsbetween apichlorohydrin
in various and theofbio-based
sectors. Most compound
these resins (phenol
(nearly or carboxylic
90%) acid),
are developed thro
and (ii) the epoxidation of C-C double bonds into oxirane.
use of epichlorohydrin and bisphenol A (in the presence of sodium hydroxide), t
As can be seen in the picture above, there are different options for the synthesis of
being a compound
bio-based that is considerably
epoxy resins. However, harmful
considering that vegetabletooils
both are health
the mostand the raw
suitable environm
For[3]this
materials andreason,
that theyone of thecontain
generally key objectives
unsaturatedhas been
double the synthesis
bonds, they are theof these res
best
candidates to promote epoxidation reactions.
natural elements. The methodology of the preparation of epoxy resins means th
pounds of related renewable origin (Figure 2) have great potential for the syn
epoxy resins, which translates into a wide range of possibilities for obtaining this
resin with bio-based content. Furthermore, it should be taken into account that
the curing reaction, the epoxy group could be ring-opened by carboxyl, anhyd
 amine. It is therefore possible to design bio-based systems using a mixture of several re-
newable curing agents. To obtain bio-based epoxy resins, there are two types of routes: (i)
Polymers 2023, 15, 2939 direct reaction between apichlorohydrin and the bio-based compound (phenol or carbox- 4 of 16
ylic acid), and (ii) the epoxidation of C-C double bonds into oxirane.

Figure 2. Renewable sources for the synthesis of bio-based epoxy resins.

Figure 2. Renewable sources for the synthesis of bio-based epoxy resins.
Due to the several renewable options through which these resins can be obtained, they
canAs be can be seen in the picture above, there are different options for the synthesis of
separated into the following groups: (i) aromatic-containing bio-based epoxy resin;
bio-based epoxy resins. However, considering that vegetable oils are the most suitable
(ii) aliphatic bio-based epoxy resin; (iii) fully bio-based epoxy resin.
raw materials [Error! Reference source not found.] and that they generally contain un-
Within the aromatic bio-based epoxy resins, different sources for their synthesis, such
saturated double bonds, they are the best candidates to promote epoxidation reactions.
as cardanol,
Due to thelignin,
severalorrenewable
gallic acid, couldthrough
options be found. which these resins can be obtained,
Cardanol is a by-product extracted
they can be separated into the following groups: from cashew nut shells that
(i) aromatic-containing contains
bio-based epoxy a hydroxyl
group, olefinic bonds in the alkyl chain, and an aromatic
resin; (ii) aliphatic bio-based epoxy resin; (iii) fully bio-based epoxy resin. ring, making it an interesting
substitute
Within the aromatic bio-based epoxy resins, different sources for their synthesis, such due to its
for bisphenol A in epoxy networks. However, it should be noted that,
asinborn
cardanol,structural
lignin, ordefects, thecould
gallic acid, aliphatic chain present in this compound, causes the glass
be found.
Cardanol
transition is a by-product
temperature values extracted from materials
of the final cashew nut toshells that than
be lower containsthosea hydroxyl
obtained in resins
group, olefinic bonds in the alkyl chain, and an aromatic
with DGEBA (Bisphenol A diglycidyl ether). With respect to the mechanical ring, making it an interestingproperties,
substitute
these arefor alsobisphenol
inferiorAtointhose
epoxyobtained
networks.withHowever,
DGEBA.it should
Thatbe is noted that, due to its
why copolymerization with
inborn structural defects,
other reactants is needed [2,9]. the aliphatic chain present in this compound, causes the glass
transition temperature values of the final materials to be lower than those obtained in
On the other hand, lignin is a very promising aromatic raw material of removable
resins with DGEBA (Bisphenol A diglycidyl ether). With respect to the mechanical prop-
origin for the development of bio-based epoxy resins, as it is one of the most abundant
erties, these are also inferior to those obtained with DGEBA. That is why copolymerization
biopolymers
with and also
other reactants has phenolic
is needed [Error! hydroxyl
Reference groups
source notthatfound.,Error!
can react with epichlorohydrin.
Reference
This compound
source not found.]. is found in most plants (present in cell walls) and is generated in large
quantities
On the as a by-product
other hand, ligninofisthe paper
a very industry,aromatic
promising among raw others. Focusing
material on its structure, it
of removable
is a complex
origin and amorphous
for the development three-dimensional
of bio-based epoxy resins,network
as it is onewhoseof thecontent varies depending
most abundant
on the typeand
biopolymers of plant,
also hasaccounting for around
phenolic hydroxyl 15–40%
groups of the
that can dry
react weight
with of the lignocellulosic
epichlorohydrin.
This compound
biomass. Due to is found in most plants
its complicated (present
structure invariation
and cell walls)in and is generated
molecular in large
weight, its industrial
quantities
applicationsas a by-product of the paper
are rather limited, industry,
as they tend among
to resultothers.
in low Focusing
yields.on its structure,
Therefore, fractionation
itor
is pre-treatment
a complex and amorphous
of lignin isthree-dimensional
currently being used network whose content
to develop varies depend- and more
low polydispersity
ing on the type of plant,
homogeneous starting materials. accounting for around 15–40% of the dry weight of the lignocel-
lulosic biomass. Due to its complicated structure and variation in molecular weight, its
With regard to the synthesis of bio-based epoxy resins, these compounds must also
industrial applications are rather limited, as they tend to result in low yields. Therefore,
be modified prior to the epoxidation process, as lignins are not soluble and have low
fractionation or pre-treatment of lignin is currently being used to develop low polydis-
functionality. The most common processes for using lignin are summarized below:
persity and more homogeneous starting materials.
• WithDirect mixing
regard ofsynthesis
to the lignin with epoxy resin;
of bio-based epoxy resins, these compounds must also
• modified
be Modification of lignin
prior to the by glycidylation;
epoxidation process, as lignins are not soluble and have low func-
tionality.
• The most common
Modification processes
of lignin for using
derivatives and lignin are summarized
subsequent below:
glycidylation.
According to the latest research by Liu et al. (2021), copolymerization of partially
depolymerized lignin is one of the most promising methods. In addition, lignin derivatives
are the most suitable for the synthesis of epoxy resins. Among them, vanillin, which
has been mentioned above in the section on benzoxazine resin synthesis, stands out.
Furthermore, apart from vanillin, another compound that stands out among others is
eugenol, as it has two functional groups, the phenolic hydroxyl group and the allyl group,
which can be modified to precursors with a variety of functionality for bio-based epoxy
resins. In comparison to traditional BPA-based (Bisphenol A-based) epoxy resins, it should
be noted that bio-based materials derived from lignin exhibit a higher limiting oxygen
index (LOI), which can translate into a more effective material in terms of fire retardancy.
Polymers 2023, 15, 2939 5 of 16

Finally, gallic acid is a compound derived from hydrolytic tannins, with three phenolic
hydroxyl groups and a carboxylic group in its structure that can be used for synthesis.
Within the aliphatic group, vegetable oils (a mixture of esters derived from glycerol
and unsaturated fatty acids) stand out as one of the main raw materials in the development
of bio-based epoxy resins, which are obtained through the epoxidation reaction with
molecular oxygen or through chemoenzymatic reactions. These include castor oil, soybean
oil, microalgae oil, and residual vegetable oil, among others [2,9]. In general, these types of
oils have been widely used for products such as cosmetics, lubricants, coatings, resins, etc.
In addition to oils, sucrose, or aliphatic polyols of biological origin, such as glycerol or
sorbitol, are other valid alternatives.
Fully bio-based resins are considered to be those systems in which the epoxy precursor
and hardener are from renewable sources. The curing agents used for the cross-linking
of epoxy resins are generally polyamines and carboxylic compounds. Therefore, in order
to be able to obtain a 100% bio-based system, one of the most attractive alternatives is to
give vegetable oils the appropriate functionality so that they can also act as hardening
agents in the system. As an example, lignin-derived curing agents can be prepared using
either of two methods: (i) the reaction of lignin with ozone in the presence of NaOH (which
provides the lignin with unsaturated carboxyl groups); or (ii) modified lignin together with,
for example, anhydrides.

2.4. Bio-Based Unsaturated Polyester Resin

Polyester resins (Ups) are obtained from the condensation of a saturated dicarboxylic
acid or its anhydride as well as an unsaturated dicarboxylic acid with dialcohols such
as ethylene glycol or propylene glycol. Once the condensation reaction has taken place,
the carbon-carbon double bonds polymerize to form a cross-linked network through the
addition of free radicals [9,12].
These resins have many advantages, such as high workability, good mechanical,
electrical, and chemical properties, and a low cost compared to epoxy resins.
In addition, in recent years, there has been increasing interest in the synthesis of these
resins using removable raw materials such as diacids and diols. For example, itaconic acid
has a carbon-carbon double bond and two carboxyl groups, so it has a high similarity to
maleic acid. It is therefore a very interesting substitute.
However, it should be noted that very few bio-based products contain at least one
benzene ring together with two carboxyl groups or two hydroxyl groups with reactivity. The
furan ring is the one that provides this type of resin with the necessary rigidity. Therefore,
in order to obtain bio-based UP resins with good thermo-mechanical properties, itaconic
acid is a good alternative. In addition to this, there are other alternatives such as resorcinol,
although this requires prior treatment due to its low nucleophilicity, or eugenol, which has
a phenolic fraction and an allyl group.
In Table 2, some natural sources are shown in order to summarize the bio-based
elements from which thermosetting resins and other substances can be obtained.

Table 2. Natural sources for the development of bio-based products.

Resource Related Chemical Functional Group Bio-Based Products

Itaconic acid Carboxyl; C-C double bond Epoxy resin; Ups; Ups reactive diluents
Carbohydrate Furfuryl amine Furan group Benzoxazine and Epoxy resin
Isosorbide Alcohols; Diheterocycles Ups; Epoxy and curing agent
Vanillin Aldehyde Benzoxazine and Epoxy resin
Lignin Benzoxazine and Epoxy resin;
Eugenol C-C double bond
Ups reactive diluents
Guaiacol
Ester group; unsaturated Epoxy resin and curing agent; Ups;
Vegetable Oils Glyceride
aliphatic chain Ups reactive diluents
Cardanol unsaturated aliphatic chain Benzoxazine; Epoxy resin
 Polymers 2023, 15, 2939 6 of 16

3. Sustainable Reinforcements
3.1. Natural Fibers
Natural fibers have demonstrated their capabilities in load-bearing applications due to
their strength and stiffness. Compared with traditional composites, natural fiber compos-
ites have attracted much attention in the industry due to their density and environmental
friendliness (https://doi.org/10.1016/j.jobe.2020.101411 (accessed on 14 May 2023)). Nat-
ural fibers consist of many elongated fibrils of cellulose and lignin, which associate with
hydrogen bonds to provide strength and inflexibility. Synthetic fibers show better me-
chanical and physical properties compared to natural fibers. The specific modulus and
elongation at break are better in natural fibers than in synthetic ones, which is considered
an important factor in polymer engineering composites [13].
Besides vegetable fibers, there are also different kinds of different animal fibers, such
as those made of wool, silk, feathers, bird fibers, and animal hair, which are the most
important resources. Straw fibers are collected from the husks and straws of crops such
Polymers 2023, 15, x FOR PEER REVIEW 7 of 18
as wheat, rice, and barley. Natural fibers can be obtained in bundles from many parts of
plants, such as bast stems, leaves, and seeds. Fiber classifications are shown in Figure 3.

Figure 3. Classification of sustainable fibers.

3.1.1. Natural Fiber-Polymer Composites

Figure 3. Classification of sustainable fibers.
Natural fiber composites are materials made of a polymer matrix embedded with
high-strength natural fibers such
3.1.1. Natural Fiber-Polymer as flax, jute, oil palm, and kenaf [14–16]. One reason for
Composites
their growing use is that natural fibers have a similar stiffness to glass fibers and higher
Natural fiber composites are materials made of a polymer matrix embedded with
strength [17]. Because of these characteristics and cheaper sources, these natural fibers offer
high-strength
advantageousnatural
strengthsfibers
andsuch as flax,
stiffness at ajute,
loweroil cost
palm, and kenaf [Error! Reference source
[18].
not found.–Error!
There are some Reference source
aspects that affectnot
thefound.]. One reason
characteristics for their growing
and performance of theseuse
kindsis that
of
natural fibers have a similar stiffness to glass fibers and higher strength
composites, such as moisture [19], the hydrophilic nature of natural fibers, and fiber load-[Error! Reference
source not found.].
ings [20–22]. Because
It is usually of these
noticed that highcharacteristics
fiber loadings and cheaper
provide goodsources, these
mechanical natural
strength.
fibers offervariable
Another advantageous strengths
to take into account and stiffness
is the at a composition
chemical lower cost [Error! Reference
of natural source
fibers. Their
not found.].
structure is normally composed of cellulose, hemicellulose, lignin, and waxes, contributing
There
to the are some aspects
characteristics that affect
of composites. the characteristics
Studies and performance
have been reported of these
on the suitability, kinds
compet-
ofitiveness,
composites, andsuch
capabilities of natural
as moisture [Error! fibers with matrixes.
Reference source notResearchers have
found.], the studied the
hydrophilic na-
compatibility
ture of natural of natural
fibers, andfibers
fiberand matrix [Error!
loadings by using various surface
Reference sourcemodification techniques
not found.–Error! Ref-
and manufacturing
erence processes.
source not found.]. It is Moreover,
usually noticed processing techniques
that high and parameters
fiber loadings provideare goodother
me-
factors affecting composites’ characteristics. The selection of appropriate
chanical strength. Another variable to take into account is the chemical composition of processing tech-
niques fibers.
natural provides the best
Their characteristics
structure is normally for producing
composedcomposites. Some
of cellulose, studies have lignin,
hemicellulose, been
done on the basis of comparative studies of natural fibers with particular
and waxes, contributing to the characteristics of composites. Studies have been reported polymers [23].
on the suitability, competitiveness, and capabilities of natural fibers with matrixes. Re-
searchers have studied the compatibility of natural fibers and matrix by using various
surface modification techniques and manufacturing processes. Moreover, processing
techniques and parameters are other factors affecting composites’ characteristics. The se-
lection of appropriate processing techniques provides the best characteristics for produc-
 Polymers 2023, 15, 2939 7 of 16

3.1.2. Hybrid Composites

Polymers 2023, 15, x FOR PEER REVIEW Natural fiber-reinforced hybrid composites are created in order to be environmentally 9 of 18
friendly and meet the demands of industries looking for sustainability. Reinforcing two
or more natural fibers into a single matrix develops a hybrid composite. There are many
researchers [24,25] who have tried to select the best combination of natural fibers to achieve
3.2.
theSustainable
best outcomeCores for utilization and minimize the negative aspects. Combinations of
Composite
different typessandwich
of fibers instructures are widely
a single matrix applied in
can generate the aerospace,
synergistic resultsmarine, trans-
and, therefore,
portation [Error!hybrid
highly valued Reference source not Basically,
biocomposites. found.–Error!three Reference source not found.],
types of reinforcement methodsand have
been incorporated:
construction industries. (1)The
a mixture
sandwich of two types of
structure short fibers
consists of twobefore adding
(top and matrix
bottom) [26],
skins oror
(2) adding
facings bonded fibers
to ainto polymer
core materialalternatively
[34]. The main layering
functiona fiber mat core
of this or fabric and matrix
material is to give[27];
(3)composite
the in the casesandwich
of glass fiber-LC fiberhigh
structures composite systems,
compressive andaddition
flexuralof nonwoven
strength, asand woven
well as
fabricrigidity,
greater in both types
withoutof reinforcements [28,29]. the overall weight of the composite ma-
significantly increasing
terial.
3.2.The
Sustainable Cores allows sandwich panels to be tailored to specific applications,
core structure
Composite
where the most commonly sandwichused structures are widely
core structures areapplied
foams in the aerospace,
[35,36] marine,
or solid cores, trans-
honey-
portation
comb cores,[30–33], and construction
truss cores, and web cores industries. The sandwich
[Error! Reference source structure consists(Figure
not found.] of two 4).
(top
and bottom)
Polymer skins for
foam cores, or facings
example, bonded
are widelyto a used
core material [34]. The
for car flooring, boatmain function
parts, of this
and turbine
core material
blades due to theiris toresistance
give the composite
to fatigue and sandwich structures
temperature, good high compressive
rigidity, and high and flexural
strength
[Error! Reference source not found.–Error! Reference source not found.]. On the otherof
strength, as well as greater rigidity, without significantly increasing the overall weight
the composite
hand, honeycomb material.
cores are suitable for aerospace [Error! Reference source not found.],
The core structure
automotive, sports, and marine allows sandwich
industries.panels to be tailored to specific applications, where
theThus,
most commonly used core
composite core materials structures
have are foams
to meet [35,36]
the or solid cores,
requirements of thehoneycomb
applicationcores,
in
trussthey
which cores, and
will be web cores
placed; [37]requirements
these (Figure 4). Polymer
may lead foam
to the cores, for example,
fulfilment are widely
of the following
used for car
properties: flooring,toboat
resistance parts, and
chemicals, turbinecorrosion,
moisture, blades due etc.toFor
their resistance
this to fatigue
reason, for and
its appli-
temperature, good rigidity, and high strength [38–41].
cation, specific materials and configurations need to be selected. On the other hand, honeycomb cores
are suitable for aerospace [41], automotive, sports, and marine industries.

Figure 4. Sandwich construction configurations.

Figure 4. Sandwich construction configurations.
Thus, composite core materials have to meet the requirements of the application in
Eventhey
which though
will many composite
be placed; these core materials may
requirements are well-established, increasing
lead to the fulfilment of theaware-
follow-
ness of environmental issues has led to the use of new sustainable materials for
ing properties: resistance to chemicals, moisture, corrosion, etc. For this reason, for its sandwich
structures [Error!
application, Reference
specific source
materials not found.]. Although
and configurations need to bethere is still a need to search
selected.
for andEvenmanufacture
though manymorecomposite
environmentally friendlyare
core materials materials, there are increasing
well-established, currently someaware-
companies, such as EconCore,
ness of environmental thatled
issues has have developed
to the use of new sustainable corematerials
sustainable materials forbased on
sandwich
natural materials.
structures [33]. Nowadays, the sustainable
Although there coretomaterials
is still a need search foravailable are wood, Poly-Lac-
and manufacture more envi-
ticronmentally
Acid (PLA), friendly materials,
and tannin, among there
others.are currently some companies, such as EconCore,
that have developed sustainable core
PLA is a biodegradable polymer obtained materials
frombased on natural
renewable materials.
sources, Nowadays,
such as sugar fer-
the sustainable
mentation core materials
or starch-rich products,available
and hasare wood,
gained Poly-Lactic
much attentionAcid (PLA),
in the andyears.
last few tannin,
Du among others.Reference source not found.] developed a bio-based sandwich structure
et al. [Error!
made of PLAbothis skin
a biodegradable polymer
and core materials fromobtained
biofiber from
andrenewable
PLA matrix. sources, such asindi-
The findings sugar
fermentation
cated or starch-rich
that the newly products,
developed materialand hasthe
met gained much attention
automotive in therequirements
specification last few years.
for load floor flexural properties. Lascano et al. [Error! Reference source not found.] have
developed a highly sustainable sandwich structure made of a PLA honeycomb core and
PLA/flax skin faces with balanced mechanical properties for medium-to-high technologi-
cal applications. Furthermore, the TU/Ecomotive team from Eindhoven University of
Technology [Error! Reference source not found.] has proven the suitability of using PLA
Polymers 2023, 15, 2939 8 of 16

Du et al. [42] developed a bio-based sandwich structure made of both skin and core
materials from biofiber and PLA matrix. The findings indicated that the newly developed
material met the automotive specification requirements for load floor flexural properties.
Lascano et al. [43] have developed a highly sustainable sandwich structure made of a PLA
honeycomb core and PLA/flax skin faces with balanced mechanical properties for medium-
to-high technological applications. Furthermore, the TU/Ecomotive team from Eindhoven
University of Technology [44] has proven the suitability of using PLA honeycomb core
from EconCore to produce the chassis, body, and interior of the world’s first car made
from biocomposites.
Balsa wood is widely used in the fabrication of wind turbine blades, boats, decks,
small aircraft, etc. [45]. It is a light and natural material known to be good for thermal and
acoustic insulation. Although the balsa core can be used as blocks or lumber, its substitution
by thin veneer layers shows improved properties. Shir Mohammadi et al. [46], for example,
demonstrated that laminated veneer lumber (LVL) balsa improved the toughness of a core
material compared to solid balsa, although it is dependent on the lamination adhesive.
Wu et al. [47] similarly confirmed the advantage of using veneered balsa wood in compari-
son to block material, since the first one reduces property scatter. Nowadays, veneer-based
core materials are commercially available as Baltek® VBC from 3A Composites. On the
other hand, Gurit® commercializes end-grain balsa wood core in a wide range of densities,
thicknesses, formats, and finishes under the trade name Balsaflex™.
Cork is a truly lightweight material and a good electric, thermal, sound, and vibration
insulator, in addition to being impermeable to gases or liquids [48]. When this material
is used as a core in a sandwich structure, it offers a high stiffness-to-weight ratio, a high
strength-to-weight ratio, thermal and acoustic insulation, etc. [49].
Sargianis et al. [50] showed that sandwich materials made of carbon fiber face sheets
and cork agglomerate as a core material provided great performance in both acoustics
and vibration. The authors claimed that these results could present a good solution in the
aircraft and aerospace industries.
In a different study, Hoto et al. [51] developed a sustainable asymmetric sandwich
material with basalt and flax natural fibers, an agglomerate cork panel as a core, and a
bio-based epoxy resin as a matrix. The results showed good energy absorption behavior
during the bending test and how the infiltration of the resin inside the core reduced the
water absorption. Additionally, Torres et al. [52] presented the mechanical performance
under tensile and flexural loads of this sandwich material composition. A longboard was
manufactured as a demonstrator, and the results to failure showed acceptable performance
for service conditions.
Amorim Cork Composites commercializes CORECORK materials made of cork gran-
ules agglomerated and free of plasticizers. The portfolio offers core materials for lightweight
composite structures and products, as well as sandwich materials for residential and indus-
trial applications.
Last but not least, polymer foams derived from diverse bio-sources, such as tannin [53],
starch [54], flax oil, etc., or recyclable processes, such as recycled PET foams [55], have
been investigated or even commercialized. It is the case of ArmaFORM PET MC foam
developed by Armacell, made from 100% post-consumer recycled PET, fully recyclable,
and with improved compression strength and impact performance.

4. Composite Recyclability
In recent years, there has been concern about the accumulation of waste composite
materials due to the vast number of wind turbines, aircraft, and boats, for example, reaching
their End-of-Life and consequently being decommissioned. Furthermore, if we think about
the ban that countries can impose on composite landfilling in the coming years, as Germany
did in 2009, the reuse and recyclability of composite materials has become necessary.
Polymers 2023, 15, 2939 9 of 16

Polymers 2023, 15, x FOR PEER REVIEW 11 of 18

This section will not describe each recycling method available for composite materials
(mechanical, thermal, and chemical recycling), but will present the most recent studies and
developments on recyclable
Liu et al. presented thermoset
a fully resins.
recyclable phenolic-based resin using commercial novolac
Liu et al. presented a fully recyclable phenolic-based resin using commercial novolac
resin and toluene diisocyanate by forming a dynamic cross-linked network [Error! Refer-
resin and toluene diisocyanate by forming a dynamic cross-linked network [56]. The
ence source not found.]. The advantage consisted of avoiding catalysts and exhibiting
advantage consisted of avoiding catalysts and exhibiting good recyclability with a high
good recyclability with a high Tg value (up to 200 °C), in addition to almost equal me-
Tg value (up to 200 ◦ C), in addition to almost equal mechanical strength even after five
chanical strength even after five crushing and molding cycles. In this case, the presented
crushing and molding cycles. In this case, the presented reversibly exchangeable topology
reversibly exchangeable topology is comparable to that of vitrimers. Vitrimers are charac-
is comparable to that of vitrimers. Vitrimers are characterized by their ability to flow
terized by their ability to flow above their topology’s freezing transition temperature, Tv
above their topology’s freezing transition temperature, Tv (the temperature at which the
(the temperature at which the material changes from viscoelastic solid to viscoelastic liq-
material changes from viscoelastic solid to viscoelastic liquid), while becoming rigid (like a
uid), while becoming rigid (like a thermoset) below it (Figure 5).
thermoset) below it (Figure 5).

Figure5.5.Schematic
Figure Schematicrepresentation
representationofofthe
thevitrimer
vitrimersystem.
system.

AsAscan
canbebeseen
seenininFigure
Figure5, 5,in
in vitrimers
vitrimers there
thereisis aa dynamic
dynamic polymerix
polymerix network
network where,
where,
below
belowthe theTv,
Tv,rigid
rigidbonds
bondsare areobtained,
obtained,so sothat
thatthe
thematerial
materialisisnot notmalleable.
malleable.On Onthetheother
other
hand,
hand, when the material is subjected to high temperatures (above its Tv), these bondscan
when the material is subjected to high temperatures (above its Tv), these bonds can
be
beexchanged
exchangedwith withothers
othersin inthe
thenetwork.
network.In Inthis
thisway,
way,the thematerial
materialcan canbebethermoformed.
thermoformed.
The
The dynamic
dynamic networks present present in invitrimer
vitrimermaterials
materialsare arebased
based onon exchangeable
exchangeable re-
reactions,
actions, such such as imine-amine
as imine-amine exchange,
exchange, transesterification,
transesterification, and disulfide
and disulfide exchange,exchange,
among
among
others.others.
The
Thefirst
firstcommercially
commerciallyavailable
availablevitrimer
vitrimermaterial
materialisisbased
basedon on imine-amine
imine-amine exchange,
exchange,
developed by Taynton et al. [57,58] under the name Vitrimax™
developed by Taynton et al. [Error! Reference source not found.,Error! and commercialized
Reference source by
Mallinda [59]. They offer diverse Vitrimax™ materials with different
not found.] under the name Vitrimax™ and commercialized by Mallinda [Error! Refer- properties (Tg values,
for example)
ence source notand found.].
orientedThey
to different manufacturing
offer diverse Vitrimax™ processes.
materials In with
orderdifferent
to understand the
properties
manufacturing
(Tg values, formethodexample)of this
andkind of material,
oriented He et al.
to different [60] recently presented
manufacturing processes.theIn network
order to
malleability, interfacial welding, and solvent-assisted recyclability of
understand the manufacturing method of this kind of material, He et al. [Error! Referencethese materials follow-
ing
source not found.] recently presented the network malleability, interfacial welding,and
the previous work of Taynton et al. [57]. It demonstrated the recyclability process and
the reusability of recyclability
solvent-assisted the recycled polyimine for the next
of these materials group the
following of composite
previous workmanufacturing.
of Taynton
et al.In[Error!
different studies,source
Reference disulfide-containing hardeners have
not found.]. It demonstrated thebeen applied process
recyclability to developand
reversible, self-healing, and malleable epoxy resins. It is the case
the reusability of the recycled polyimine for the next group of composite manufacturing.of the work presented
by Zhang et al. [61], in which 1,4,5-oxadithiepane-2,7-dione (DSAA) was designed and
In different studies, disulfide-containing hardeners have been applied to develop re-
synthesized to be used as a hardener along with methylhexahydrophthalic anhydride
versible, self-healing, and malleable epoxy resins. It is the case of the work presented by
(MHHPA) as a co-curing agent. The developed resin showed high mechanical strength and
Zhang et al. [Error! Reference source not found.], in which 1,4,5-oxadithiepane-2,7-dione
good thermal resistance (Tg of 113 ◦ C), meeting the requirements for electronic packaging,
(DSAA) was designed and synthesized to be used as a hardener along with methylhexa-
in addition to good malleability and reversible self-healing ability. Preliminary tests about
hydrophthalic anhydride (MHHPA) as a co-curing agent. The developed resin showed
the recyclability process have also been presented, although it still needs to be improved.
high mechanical strength and good thermal resistance (Tg of 113 °C), meeting the require-
ments for electronic packaging, in addition to good malleability and reversible self-
 healing ability. Preliminary tests about the recyclability process have also been presented,
although it still needs to be improved.
Since 2016, extensive work has been undertaken using aromatic disulfide bonds to
Polymers 2023, 15, 2939 10 of 16
crosslink epoxy resins and develop a new generation of fiber-reinforced thermoset com-
posite materials with good (re)processability, reparability, and recyclability [Error! Refer-
ence source not found.,Error! Reference source not found.]. The processability/reshaping
was provenSince and2016,compared
extensive to work has beenthermoset
a reference undertaken using aromatic
material, in whichdisulfide
the newly bonds
devel-
to crosslink epoxy resins and develop a new generation of fiber-reinforced
oped material showed good processability in a hot press at 200 °C at 100 bar for 5 min. thermoset
composite materials with good (re)processability, reparability, and recyclability [62,63]. The
Furthermore, the mechanical recycling of such material was also presented, showing com-
processability/reshaping was proven and compared to a reference thermoset material, in
parable mechanical properties to the reference material after the recycling process. Re-
which the newly developed material showed good processability in a hot press at 200 ◦ C
cently,
at 100 bar for 5 min. Furthermore, the mechanical recycling of such material was also°C)
the same group obtained an aero grade epoxy resin with high Tg values (175
while being sustainable
presented, [Error! Reference
showing comparable mechanicalsource not to
properties found.]. The solution
the reference materialto reaching
after the
higher Tg values comes from the idea of introducing some fraction
recycling process. Recently, the same group obtained an aero grade epoxy resin with high of permanent cross-
links
Tg (up
valuesto 30%) ◦
(175 in C) order not tosustainable
while being lose the reprocessability
[64]. The solution of to
thereaching
material.higher Tg values
Following
comes from the theidea
idea of of recyclingsome
introducing epoxy resins,ofitpermanent
fraction has been crosslinks
extensively (updemonstrated
to 30%) in
thatorder
it is not to loseto
possible the reprocessability
recycle epoxy-basedof the material. materials to recover at least the rein-
composite
forcementsFollowing
while the idea of
keeping recycling
their epoxyItresins,
properties. is the itcase
hasofbeen
the extensively
Recyclamine™ demonstrated
technology,
originating from Connora Technologies and acquired by Aditya Birla in least
that it is possible to recycle epoxy-based composite materials to recover at 2019.the
Therein-
recy-
forcements while keeping their properties. It is the case of the Recyclamine™
cling process is based on placing the composite in a dilute acetic acid solution at approxi- technology,
originating from Connora Technologies and acquired by Aditya Birla in 2019. The recycling
mately 70–80 °C for 1 h. After this time, the reinforcements are separated, filtered, and
process is based on placing the composite in a dilute acetic acid solution at approximately
cleaned to remove as much acetic acid as possible [Error! Reference source not found.].
70–80 ◦ C for 1 h. After this time, the reinforcements are separated, filtered, and cleaned to
Theremove
recycled thermoplastic
as much acetic acidepoxy mixture
as possible [65].isThe
thenrecycled
neutralized with NaOH
thermoplastic epoxy base, and after
mixture is
its then
precipitation, the mixture is filtered, rinsed, and dried (Figure 6). The
neutralized with NaOH base, and after its precipitation, the mixture is filtered, rinsed, approximated
properties
and dried of(Figure
the recovered epoxy-thermoplastic
6). The approximated properties areofprovided
the recoveredin Table 3.
epoxy-thermoplastic
are provided in Table 3.

Figure 6. Recycling process of epoxy-based resin crosslinked with Recyclamine™.

Figure 6. Recycling process of epoxy-based resin crosslinked with Recyclamine™.
Table 3. Average of properties of the recovered epoxy-thermoplastic vs. conventional bio-based
epoxy
Table with Recyclamine™
3. Average [65,66].
of properties of the recovered epoxy-thermoplastic vs. conventional bio-based
epoxy with Recyclamine™ [Error! Reference source not found.,66].
Recovered Conventional Bio-Based
Epoxy-Thermoplastic
Recovered Epoxy-Thermo- Epoxy Bio-Based
Conventional
Properties Value
plastic Value
Epoxy
Glass transition
Propertiestemperature (Tg) 40–60 ◦ C
Value 105
Value
Melting temperature (Tm) 120–140 ◦ C -
Glass transition temperature
Tensile modulus 2.4 GPa 2.8–3.2105
GPa
40–60 °C
(Tg) strength
Tensile 57 MPa 75 MPa
Elongation (Tm)
Melting temperature 45%°C
120–140 5–8%-
Shore D hardness 80 -
Polymers 2023, 15, 2939 11 of 16

As can be seen in Table 3, if the recovered epoxy thermoplastic is compared to a

conventional bio-based epoxy resin, properties such as elongation and Tg decrease consid-
erably. However, with respect to modulus and tensile strength, we see that there is a slight
decrease. Nevertheless, the properties are still good.
Thanks to the fully recyclable epoxy resin system, more sustainable composite materi-
als have been developed. It is the case of the work presented by Cicala et al. [67], in which
bio-based resins alongside hybrid flax/carbon fibers were used to manufacture hybrid
and recyclable composites. Furthermore, the reprocessing possibilities of the recycled
thermoplastic with both a microinjection molder and a single-screw extruder to produce
filaments for fused deposition modeling (FDM) processing are described, showing good
mechanical properties.
In a similar study, Ferrari et al. showed the possibility to recycle bio-based thermoset
composites derived from waste flours [66]. This research opens the opportunity to recycle
organic waste, minimizing the negative impacts on the environment.
In 2014, Arkema started the production of the liquid thermoplastic Elium® resin. This
resin is based on acrylic monomers, which have similar properties to thermosets but are
easily recyclable. Its main advantages are the liquid state, which facilitates its processability
like thermoset resins, the ability to polymerize at room temperature and harden more
quickly, and the possibility of being easily recycled in contrast to thermoset resins [68].
In the investigations carried out by Gebhardt et al. [69], they used a matrix composed of
virgin Elium® and Elium® mixed with different percentages of recycled Elium® already
polymerized in the form of granules. After a dissolution process and the manufacture of
CFRP laminates, these were compared with those made from 100% virgin Elium® and
resulted in good mechanical properties. Furthermore, in order to recycle these materials,
this type of resin can be both reprocessed and recycled by solvolysis with a common solvent.
Another recently developed alternative is the Akelite resin, patented by CSIC. This sys-
tem is an acrylic resin with good mechanical properties and the ability to be thermoformed
once cured, as well as being recyclable by immersion in acetone [70].
Among the thermoforming options, the epoxy systems from Cecence [71] also stand
out, as they can be used in a wide range of sectors due to their properties. Specifically, there
are three systems on the market: K_Chip, K_Plate, and K_Rod, which have considerably
low molding temperatures as well as swirling of the cured part.
Finally, one of the new developments that is not yet available on the market is the
SWANCOR system known as “EzCiclo”, which is an epoxy resin with the capacity to be
recycled by solvolysis with the solvent “Cleaver”, which allows the recycled resin resulting
from the process to be reused.

5. Applications
Biocomposites applications in sectors such as the automotive sector have experienced
exponential growth in Europe, as according to European regulations (EURO 6) in 2020,
those cars that generate CO2 emissions above 95 g/km will receive a penalty [72]. Therefore,
the use of biocomposites in this type of sector helps reduce these emissions. In fact, it
should be noted that, in addition, the European Directive 2000/53/EC has established the
objective of recycling 95% by weight of automobiles, creating a value chain with the use of
biocomposites.
With regard to the different sectors that make use of this type of material, the following
stand out [72]:
Tissue Engineering
This type of material is used in bone regeneration. Generally, biodegradable materials
with good mechanical properties are used. In fact, porous nanomaterials have recently
been developed for use in tissue engineering, as polymeric materials do not interfere with
cell growth.
Advanced Electronic Devices
 als with good mechanical properties are used. In fact, porous nanomaterials have recently
been developed for use in tissue engineering, as polymeric materials do not interfere with
cell growth.
Advanced Electronic Devices
Polymers 2023, 15, 2939 Within the electronics sector, multifunctional biocomposites are used for the12fabrica- of 16
tion of innovative devices such as medical devices, displays, sensors, etc. A clear example
of this are cellulose nanofibers, which are used in the manufacture of wiring, etc.
Automotive
Within the electronics sector, multifunctional biocomposites are used for the fabrication
Compared to conventional composites, biocomposites are lighter in weight. For this
of innovative devices such as medical devices, displays, sensors, etc. A clear example of
reason,
this are they are used
cellulose in the which
nanofibers, automotive sector,
are used in theasmanufacture
they provide of awiring,
reduction
etc. in CO2 emis-
sionsAutomotive
and significant fuel savings. Generally, these types of materials are used in vehicle
interiors (dashboards,
Compared door panels,
to conventional etc.), mainly
composites, due to their
biocomposites strength
are lighter and theFor
in weight. moisture
this
absorption
reason, theyofarenatural
used infibers.
the automotive sector, as they provide a reduction in CO2 emissions
Other applications
and significant fuel savings. Generally, these types of materials are used in vehicle interiors
In addition
(dashboards, doortopanels,
the sectors aforementioned,
etc.), mainly due to theirbiocomposites
strength and the have started
moisture to be used
absorption of in
aircraft
natural interior
fibers. panels, wind blades, and some housing elements, such as flooring, roof
panels,Other
andapplications
door frames, among others.
In addition to the sectors aforementioned, biocomposites have started to be used in
aircraft interior
Biocomposites panels,
Market Sizewind blades, and some housing elements, such as flooring, roof
panels, and door frames, among others.
Currently, as discussed in Section 2.3. above, epoxy resins with a bio-based content
of around
Biocomposites30% are available,
Market Size which have a considerably lower environmental impact.
Such systems and other types of bio-based resins are already being used in numerous
Currently, as discussed in Section 2.3 above, epoxy resins with a bio-based content of
applications
around 30% are together withwhich
available, natural
havereinforcements
a considerablyinlower
various sectors such
environmental as aerospace,
impact. Such
automotive, and electronics for secondary applications. Additionally, the
systems and other types of bio-based resins are already being used in numerous applications use of biocom-
posites
togetheriswith
expected to reinforcements
natural increase in thein coming
variousyears.
sectorsInsuch
fact, as
according
aerospace,to automotive,
a study published
and
by [Error! Reference
electronics for secondarysource not found.,Error!
applications. Reference
Additionally, the use source not found.]
of biocomposites during the
is expected
period 2018–2030,
to increase the composites
in the coming market
years. In fact, was valued
according at USD
to a study 24.59 billion
published (Figure
by [72,73] during 7) in
2021 and is expected to increase at a CAGR (Compound Annual Growth
the period 2018–2030, the composites market was valued at USD 24.59 billion (Figure 7) in Rate) of 16.1%.
2021 and is expected to increase at a CAGR (Compound Annual Growth Rate) of 16.1%.

Figure 7. Biocomposites market development.

Figure 7. Biocomposites market development.
In fact, developed countries such as Germany, the US, and Japan are increasingly
In fact,
focusing developed
on the countries
use of more such products
sustainable as Germany, the US, recyclability.
that promote and Japan are increasingly
focusing on the use of more sustainable products that promote recyclability.
In order to use such materials in other, more novel applications, it is vital to identify
the processing techniques and conditions, as well as the properties of the matrices, fibers,
and their interfaces. Thus, for the development of biocomposites, it is essential to have
prior knowledge of the constituent materials in order to achieve the properties demanded
by each of the sectors and applications.

6. Conclusions
Throughout the review, sustainable alternatives to conventional thermoset systems
have been analyzed. As has been observed, there are currently several alternatives to
reduce the environmental impact of composite materials. However, it is still necessary to
Polymers 2023, 15, 2939 13 of 16

invest in research in order to obtain thermosetting resins with a higher bio-based content
and, at the same time, provide similar properties to resins from fossil sources.
On the other hand, with respect to recyclable and/or thermoformable systems, these
have very interesting properties, as most of them have similar properties to the initial
ones once the recycling process has been carried out. However, other systems, such as
Recyclamine, mentioned above, lead to the possibility of using the recycled material in a
second life where the thermoplastic material has a place.
In conclusion, it is considered that the advances made in terms of sustainability do
present an important improvement, but it is necessary to look for other alternatives in
future actions that address the environmental problem in a more complete way.

Author Contributions: Conceptualization, P.A.-E. and A.I.; methodology, P.A.-E., A.I. and R.S.-
R.; validation, P.A.-E., I.G. and K.G.; formal analysis, R.S.-R. and I.G.; investigation, P.A.-E.; re-
sources, P.A.-E., A.I. and R.S.-R.; data curation, A.I.; writing—original draft preparation, P.A.-E.;
writing—review and editing, P.A.-E., A.I. and R.S.-R.; visualization, K.G. and I.G.; supervision, K.G.
and I.G.; project administration, P.A.-E.; funding acquisition, R.S.-R. All authors have read and agreed
to the published version of the manuscript.
Funding: This research was funded by the Provincial Council of Bizkaia by its Technology Transfer
Program 2021 (BIOKONP Project, Reference 6/12/TT/2021/) and by Department of Economic
Development and Infrastructures of The Basque Government by its ELKARTEK 2022 Program
(FRONTIERS Project, Reference KK-2022/00109).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: The data reported in this study are available upon request from the
corresponding author.
Acknowledgments: The authors would like to thank both the Provincial Council of Bizkaia and the
Basque Government for the funding provided.
Conflicts of Interest: The authors declare no conflict of interest.

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