International Journal of Biological Macromolecules 187 (2021) 624–650

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International Journal of Biological Macromolecules

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

Review

The role of lignin and lignin-based materials in sustainable construction – A

comprehensive review
Patryk Jędrzejczak a, Maurice N. Collins b, c, Teofil Jesionowski a, Łukasz Klapiszewski a, *
a
Poznan University of Technology, Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, PL-60965 Poznan, Poland
b
School of Engineering and Bernal Institute, University of Limerick, Ireland
c
Advanced Materials and BioEngineering Research Centre (AMBER), University of Limerick, Ireland

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

Keywords: The construction industry in the 21st century faces numerous global challenges associated with growing concerns
Functional materials for the environment. Therefore, this review focuses on the role of lignin and its derivatives in sustainable con­
Sustainable construction struction. Lignin's properties are defined in terms of their structure/property relationships and how structural
Lignin and lignin-based materials
differences arising from lignin extraction methods influence its application within the construction sector. Lignin
Concrete additives
and lignin composites allow the partial replacement of petroleum products, making the final materials and the
entire construction sector more sustainable. The latest technological developments associated with cement
composites, rigid polyurethane foams, paints and coatings, phenolic or epoxy resins, and bitumen replacements
are discussed in terms of key engineering parameters. The application of life cycle assessment in construction,
which is important from the point of view of estimating the environmental impact of various solutions and
materials, is also discussed.

1. Introduction
The construction industry accounts for 40% of global CO2 emissions,
arising from the processes implemented, and indirectly from the power
demand of this sector [1]. It is well known that reducing CO2 content in
the atmosphere is crucial in terms of achieving our planetary objectives
for sustainable development. Moreover, the construction industry has
tremendous ecological impact due to the amount of natural resources it
consumes, as well as the huge amount of waste it generates [2].
With an ever-increasing global population, estimated to exceed 9.7
billion by 2050 [3], there is an enormous and increasing demand for
social amenities, such as housing, sanitation and motorways, which
leads to further pressure points on the sustainability of the construction
industry [4]. Therefore, there is considerable urgency and demand for
materials that can enable a reduction of the overall environmental
impact of the construction industry while improving sustainability. One
approach is to utilize industrial waste, such as fly ash, silica ash, de­
molition concrete, plastics or recycled tires [2,5] and lignocellulose
waste from agricultural/forestry waste streams, such as oil palm shells,
rice husks, corn cobs or tobacco, as blends or as building blocks for new
and sustainable materials [6].
Lignin is the most abundant aromatic polymer found in nature. It is a
waste product from industrial processes, mainly the paper and pulp
industry, where small amounts are used as a low-value energy source.
The recent emergence of biorefineries has resulted in the production of
further lignin with no obvious route for valorization [7,8]. New valo­
rization routes for lignin include the production of carbon fibers [9–11],
plastics with designable properties, polymer foams, fuels and other
valuable chemical compounds [7,12]. Lignosulfonates, which are lignin
derivatives, have also found widespread application as concrete ad­
mixtures and additives [8].
Lignin-based materials have been the subject of previous reviews
that have focused on their application in the production of sustainable
rigid polyurethane foams and blends [13,14], and as modifiers or fillers
for bitumen [15]. However, this review focuses on the latest strategies
for the valorization of lignin and its derivatives in sustainable con­
struction. We discuss the relationships between lignin's structure and
properties, and how they impact on applications of lignin within the
construction sector.
The second section overviews life cycle analysis techniques with
regard to the construction industry. The third section defines lignin's
structure, sources and extraction methods. The fourth section discusses
lignin-based concrete in detail and its suitability for the construction
industry. This is followed by a section which describes the emergence of

* Corresponding author.
E-mail address: lukasz.klapiszewski@put.poznan.pl (Ł. Klapiszewski).

https://doi.org/10.1016/j.ijbiomac.2021.07.125
Received 11 May 2021; Received in revised form 8 July 2021; Accepted 19 July 2021
Available online 21 July 2021
0141-8130/© 2021 Elsevier B.V. All rights reserved.
P. Jędrzejczak et al.
lignin-based polyurethane foams as insulating materials. Next, the latest
developments relating to lignin corrosion inhibitors, protective coatings,
and resins are assessed. The following section describes the latest tech­
nologies behind asphalt pavements. Finally, we offer an outlook for a
more sustainable future for the construction industry.
2. Lignin sources, structure/property relationships
Lignin is a constituent of wood, together with cellulose and hemi­
cellulose. The percentage share of lignin in lignocellulosic raw materials
is between 10% and 35%, depending on source (see Table 1). Lignin
covers cellulose fibers that are arranged cylindrically in a wood cell
[16–23].
Lignin is composed primarily of aromatic alcohols: p-coumaryl,
coniferyl and sinapyl. Their distinguishing feature is the number of
methoxy groups. With increased methoxy groups, crosslinking becomes
easier [16,20–25]. Lignin is synthesized by dehydrogenative polymeri­
zation of hydroxyl cinnamyl alcohol monomers called monolignols (p-
coumaryl, coniferyl, and sinapyl alcohol). The vast majority of technical
lignin is obtained from the paper and pulp industry, where it is essen­
tially a by-product used in low-value energy applications. Lignin can be
classified according to the industrial pulping processes used for its
isolation (kraft, sulfite, soda, and organosolv).
The sequence of reactions that produces a lignin macromolecule in a
plant cell is one of the most energy-consuming biosynthetic processes
[26]. The pathway of synthesis and enzymatic polymerization of mon­
olignols in lignin is called the ‘phenylpropanoid pathway’ and has been
the subject of many years of research involving numerous research
groups [20,27,28]. However, despite the numerous studies, lignin has
still not been fully characterized structurally. An overview of lignin
structure is shown in Fig. 1.
Adler [29] and Freudenberg [30] have proposed possible lignin
monomer network interaction models. They believe that the monomer
composition is interconnected via a network of ether and carbon–carbon
bonds, which are formed as a result of radical polymerization
[16,20,22,28,31]. The ether bond β-O-4 accounts for the largest pro­
portion of these, with its content in lignin amounting to approximately
40–50%, regardless of the origin of the lignin. The β-β carbon–carbon
bond is the second most prevalent [16–18,20].
Research on lignin has been intensified over recent years, confirming
that this biopolymer is a valuable chemical compound. Lignin is the only
renewable raw material abundant in nature which, in addition, consists
of aromatic monomers. For this reason, lignin depolymerization is an
interesting path towards obtaining a wide range of valuable aromatic
compounds [20].
The practical application of lignin is hindered by its complex struc­
ture and the lack of repeatability, as well as the still insufficiently
developed technologies for utilizing lignin [20]. Hence, in recent years,
scientific research has concentrated on the transformation of lignin into
other substances and/or materials/biomaterials with high added value,
as well as fuels/biofuels, including syngas, carbon fibers, phenolic
compounds and multifunctional hydrocarbons [32,33]. In the light of
the above, the research effort should be focused on an attempt to study
lignin thoroughly in bioengineering terms so that its acquisition and
conversion are facilitated [18].
Both mechanical and chemical processes can be used for isolating
lignin from a lignocellulosic raw material. These approaches can be
Table 1
Cellulose, hemicellulose and lignin content in different plant types, based on
[23].
Raw material Cellulose (%) Hemicellulose (%) Lignin (%)
Hardwood 40-55 24-40 18-25
Softwood 45-50 25-35 25-35
Grass 25-40 35-50 10-30
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International Journal of Biological Macromolecules 187 (2021) 624–650
classified into two groups: (i) methods where cellulose and hemicellu­
lose are removed by way of solubilization, leaving lignin as an insoluble
residue; (ii) processes where lignin is dissolved and removed, while the
aforementioned polysaccharides constitute an undissolved residue [35].
Lignin as a material for processing may or may not contain sulfur (see
Fig. 2). Sulfur content is an important parameter that impacts the final
application of lignin. The group of sulfur-containing lignins includes
kraft lignin (KL) and lignosulfonates (LS), produced primarily within
industrial lignocellulose pulping processes. The second type includes,
among others, soda and organosolv lignin [36]. Kraft lignin is created in
a process bearing the same name [13]. The lignin obtained by such a
process has a sulfur content of 1.5–3% by weight, is soluble at pH > 10,
and exhibits high purity [36]. Moreover, it contains some aliphatic thiol
groups, which give it a characteristic odour, noticeable especially during
heat treatment [37]. Kraft lignin is hydrophobic, and therefore needs to
be modified to improve its reactivity [38]. In turn, lignosulfonates are
produced in the course of sulfite pulping. They have a highly cross-
linked structure, a sulfur content of approximately 5%, and two
ionizing group types, namely sulfonic and phenolic hydroxy groups.
Lignosulfonates are soluble over a wide pH range. Due to the sulfur
content in LS and KL, their main application is as fuels in heat and
electricity generation [38].
The second group includes lignins that do not contain sulfur within
their structure (see Fig. 2). The first type in this group is soda lignin (SL),
formed through a pulping process with the same name. This method is
applied primarily to produce lignin from annual plants and plant waste,
sources with relatively low lignin content [37,39]. Soda lignin has
higher purity and lower molecular weight (800–3000 g/mol) than kraft
lignin (1500–5000 g/mol), not to mention lignosulfonates, which have
very high molecular weights (15,000–50,000 g/mol) [39]. Soda lignin
also exhibits high silicate and molecular nitrogen content [40]. Another
variety that does not contain sulfur is organosolv lignin (OL), obtained
through biomass pulping processes, which utilize mixtures of solvents or
organic solvents with water [40]. Organosolv lignin has a low molecular
weight (500–5000 g/mol) [39] and is soluble in alkaline systems, and
also in most organic polar solvents. Nonetheless, OL does not dissolve in
acidic aqueous solutions [28,36]. Organosolv lignin is more homoge­
neous than the alkaline varieties (KL, LS, SL), and also has higher
chemical purity [40]. The great advantage of OL is that it is obtained in
an intact form, relative to the compound found naturally in plants [41].
The last major sulfur-free lignin variety is steam-explosion lignin (SEL).
Compared with KL, it exhibits higher solubility in organic solvents and
lower molecular weight [28,36]. Besides the five main lignin types listed
and briefly described above, there is also milled wood lignin (MWL),
pyrolytic lignin (PL) and hydrolytic lignin (HL). Furthermore, the
development of bio-solvent technologies in recent years has enabled the
creation of two more types of lignin, namely lignin extracted using ionic
liquids and deep eutectic solvents [20,28,36].
To improve its range of application, lignin is often subjected to
various modifications, performed mainly to create advanced systems
with unique properties [42–46]. Three main modification types are
distinguished: (i) lignin fragmentation or depolymerization so as to use
lignin as a carbon source or to break its structure down into aromatic
monomers; (ii) modification through the creation of new chemically
active locations; (iii) chemical modification (for the most part) of its
hydroxyl groups [47].
Controlled modification of lignin's structure using various com­
pounds, mainly inorganic, enables the production of functional systems,
including hybrid materials, for specialized applications [48,49].
Furthermore, new research trends include the utilization of ionic liquids
for selective lignin extraction and recovery [20,50–52].
3. Lignin-derived materials
Lignin and its modified forms, as well as advanced materials based
on lignin, have a variety of applications. Such systems have been
P. Jędrzejczak et al.
Fig. 1. Example of lignin structure with marked monolignols and the most frequent bonds, reproduced with permission [34].
Copyright 2016, Elsevier.
Fig. 2. Lignin extraction/isolation processes with a description of their main conditions, HBA – hydrogen-bond acceptors, HBD – hydrogen-bond donors, reproduced
with permission [36].
Copyright 2020, Elsevier.
adopted as effective sorbents for metal ions harmful to the environment
[48,53–57], eco-friendly and functional polymer fillers [58–62], addi­
tives to abrasive tools [63–66], pharmaceuticals [67–71], drug delivery
systems [72], and electrochemically active materials or sensors/bio­
sensors [49,73–79], and are used in the manufacture of various chem­
icals, including adipic acid [80] vanillin [81], cycloalkanes, phenols, as
well as other aromatic and aliphatic compounds [7,17]. The resulting
chemical compounds can be utilized for synthesizing other products; for
example, vanillin was used to obtain an amine hardener and an epoxy
cross-linker [82]. In addition, the selection of lignin with an appropriate
structure, rich in β-O-4 bonds, enables the synthesis of carbon fibers with
better mechanical and electrically conductive properties [83]. Technical
lignin subjected to esterification and then fractionation enables the
obtaining of sustainable bio-plastics and materials with properties
tailored to specific applications [84]. Lignin-based biodegradable com­
posite film materials can be used in areas such as sensors, responsive
materials, energy storage systems, functional packaging and biomedical
materials [85]. Facile regenerated lignin from lignocellulosic biomass
can also be used to synthesize bio-plastics with high mechanical
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International Journal of Biological Macromolecules 187 (2021) 624–650
strength, improved thermal stability, excellent water stability and
resistance to UV radiation [86]. The introduction of lignin esters into the
poly(butylene adipate-co-terephthalate) matrix enables the synthesis of
biodegradable composites providing protection against UV radiation
and having controllable mechanical properties, with potential applica­
tions in the production of packaging [87]. Moreover, lignin can be used
to produce flocculants with a low carbon footprint for wastewater
treatment [88]. Also worthy of note are lignin-based nanomaterials
produced by solution self-assembly in an organic solvent–water mixture,
which are among the most attractive products made from biomass [89].
Furthermore, lignin can be used to produce various electrode materials,
such as hierarchical porous carbon monolith [90–92], nanoporous car­
bon [93,94], interconnected hierarchical porous nitrogen-doped carbon
[95], and energy storage materials [96,97], as shown in Fig. 3.
The widespread use of lignin and its derivatives in sustainable con­
struction, for example, as cement composite additives, raw material for
rigid polyurethane foams, anti-corrosive and protective coatings, resins,
and a substitute for bitumen in asphalt production, will be discussed in
the subsequent sections.
P. Jędrzejczak et al.
Fig. 3. Applications of lignin and lignin-based materials, based on [42–97].
3.1. Lignin-based concrete admixtures and additives
A necessity in modern concrete compositions is the incorporation of
plasticizers to enhance composite workability without increasing the
water–cement (w/c) ratio. They can decrease the water content in a
concrete mix, while maintaining appropriate fluidity. Owing to the
reduced w/c ratio, the obtained concrete exhibits better strength and
durability [98]. This section discusses substances that produce unique
properties when added to a concrete mix. They generate electrostatic
action, hence contributing to steric hindrance and the formation of a
layer with lubricating properties between cement particles [99]. Water-
reducing substances are generally divided into plasticizers and super­
plasticizers [100]. In the case of the former, the degree of water
reduction is up to 12%, while for the latter it exceeds that threshold.
There are numerous plasticizers available on the market, with ligno­
sulfonates having been commonly used for more than 80 years [98].
These can be obtained from, among others, sulfite liquor or through
alkaline lignin sulfonation [99].
One of the first studies that focused on applications of two types of
lignin, namely lignosulfonates and sulfonated kraft lignin, was pub­
lished in 1958 [101]. The lignins in raw state, i.e., not subjected to any
modifications, had the ability to reduce water by up to 8% [98].
More recently, Ouyang et al. studied the properties of calcium
lignosulfonate. They discovered that its inclusion improved the physical
and chemical properties of cement, and that it exhibited adsorptive
capacity on cement particle surfaces, surface activity, and foam gener­
ation potential. This effect was correlated with increasing molecular
weight of the lignosulfonate. In the case of the zeta potential, which is a
characteristic of a cement particle's surface charge, higher values were
obtained for low and intermediate molecular weights. The greatest
improvement in the workability of cement was obtained for a calcium
lignosulfonate fraction with a molecular weight of 10,000–30,000 g/
mol. In contrast, lignosulfonate with a higher molecular weight pro­
duced a stronger aerating effect, which negatively affects the compres­
sive strength of concrete [98].
Subsequently, calcium lignosulfonate was subjected to modifica­
tions: oxidation and sulfonation. The resulting product was shown to
increase overall zeta potential, reduce surface tension so as to increase
wetting ability, and improve adsorption, while its workability and
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International Journal of Biological Macromolecules 187 (2021) 624–650
compressive strength were comparable to those of contemporary com­
mercial products [98].
Sodium lignosulfonate was also subjected to oxidation and modifi­
cation processes with the purpose of verifying its impact on the prop­
erties of concrete. Peracetic acid was used as the oxidizing agent, and
iron(II) sulfate(IV) as the catalyst. In the next stage lignosulfonate was
sulfomethylated through contact with sodium sulfate(IV) and formal­
dehyde. This work showed that the oxidization of lignosulfonate, fol­
lowed by its modification, increased cement fluidity by almost 15%
[99].
Beyond the study of lignosulfonates in terms of their behavior in
concrete admixtures, Li et al. extracted lignin from pinewood through
contact with formic acid, which was then fractioned by adding various
organic solvents [102]. The aforementioned extraction process led to
high-purity lignin with low contents of sulfur (below 0.5% wt.) and ash
(below 0.2% wt.), and without nitrogen. Fractionation led to two types
of lignin: soluble lignin with low molecular weight, and insoluble lignin
with high molecular weight. Both fractions were then oxidized with
hydrogen peroxide. This was followed by sulfomethylation using form­
aldehyde and sodium sulfate(IV). It was found that the fractionated
lignin that had been subjected to oxidization and sulfomethylation was
more potent at improving cement workability than the extracted lignin.
Further study confirmed the higher number of reactive sites in the
molecules of lignin when divided into fractions; this facilitates its
modification, hence improving its efficiency as a superplasticizer [102].
Another type of lignin studied to verify its impact on concrete mixes
is a variety obtained through biorefining, where it is considered as
waste, similar to the situation in the pulp and paper industry. Lignin can
be found in solubilized form in the pre-treatment liquor that generates
alkaline lignin through acidification [103] and as a solid – the product of
enzymatic hydrolysis [104]. Lignin originating from the pulp and paper
industry has already found various applications, while there are still no
interesting and beneficial applications for the lignin that constitutes
lignocellulose mass biorefining waste [105].
In their research, Huang et al. subjected both alkaline lignin and
enzymatic hydrolysis lignin to sulfomethylation. Next, the obtained
lignosulfonates were added to cement paste, which improved its fluidity.
These products also exhibit higher water-reducing capacity than do
commercially available lignosulfonates. Furthermore, adding 0.1% or
P. Jędrzejczak et al.
0.2% wt. of lignosulfonates was found to improve the 28-day compres­
sive strength of concrete. However, higher doses of the lignin additive
led to greater mixture aeration, and hence weakened the resulting
concrete structures [103].
Kraft lignin has also been added to concrete, and the impact of this on
the resulting composite material has been assessed via cement flow­
ability and workability. Prior to using kraft lignin as an additive to the
cement mix, it was subject to controlled radical polymerization with
reversible fragmentation, combined with chain transfer, which resulted
in a kraft lignin derivative with grafted polyacrylamide fragments
(LPAM). It was found that LPAM significantly reduced the cement paste's
yield point, and hence improved its workability [106].
A smaller, but still clear impact of modified lignin on the afore­
mentioned parameter was observed in the case of samples with mineral
additives in the form of kaolin and clinoptilolite (used to reduce
greenhouse gas emissions in cement production). While these additives
alone reduced concrete mix fluidity, LPAM with kaolin or clinoptilolite
had a significant positive impact on the workability of the cement paste.
The results were similar to those obtained for currently used commercial
admixtures, while simultaneously introducing ten times less additives
[106].
The application of soda lignin, yet another lignin variant, was stud­
ied by Kalliola et al. Here, it was first oxidized with O2 in an alkaline
environment to enable the control of polymerization and solubilization.
Oxidized lignin solutions were then used as concrete plasticizers. A se­
ries of tests demonstrated that they were more effective than the lig­
nosulfonates currently used in the construction industry. Indeed, the
concrete plasticization capacity provided by 0.4% wt. of oxidized lignin
Fig. 4. Reactions taking place during modification of lignin with diethanolamine (a), reproduced with permission [109]. Copyright 2014, Elsevier. Graphical
presentation of the retarding mechanism of diethanolamine modified lignin, as a cement grinding aid, DML – diethanolamine modified lignin (b), reproduced with
permission [109].
Copyright 2014, Elsevier.
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International Journal of Biological Macromolecules 187 (2021) 624–650
was comparable to that obtained in the case of commercial products
used in an amount of 0.2% wt. Furthermore, it was found that on
addition of a modified lignin solution, the aeration phenomenon that
negatively affects concrete's compressive strength did not occur [107]
(this effect is one of the major disadvantages of using lignosulfonates as
an admixture for this composite [108]). What is more, the use of
oxidized lignin had no negative impact on the compressive strength of
the cured concrete [107].
In turn, Li et al. used lignin modified using epichlorohydrin and
diethanolamine. The reactions occurring are shown in Fig. 4a. As a result
of this process, a diethanolamine modified lignin (DML) was obtained,
which was then used for the production of Portland cement. The
research showed that the addition of DML has a positive effect on the
grinding efficiency and improves the particle size distribution. It was
also found that the introduction of modified lignin into the cement
mortar improves its mechanical properties at all stages of hydration.
Compared to lignin, DML exhibits very strong retarding properties for
both the initial and final setting time. This fact was linked to the
occurrence of steric hindrance in molecular structures and electrostatic
interactions between anchoring groups absorbed on the cement surface,
which arise during its hydration. The above-mentioned phenomenon is
shown graphically in Fig. 4b [109].
A team led by Klapiszewski investigated the creation of completely
new, functional lignin-containing hybrid materials. The proposed me­
chanical synthesis led to two lignin–alumina hybrid materials: kraft
lignin–Al2O3 and magnesium lignosulfonate–Al2O3. These systems were
then used in concrete admixtures to improve their properties. The
effective synthesis of the hybrid system was confirmed by infrared
P. Jędrzejczak et al. International Journal of Biological Macromolecules 187 (2021) 624–650

spectroscopy. Fourier transformation studies led to the conclusion that Table 2

in standard concrete admixtures weak hydrogen interactions existed Summary of lignin and its derivatives as admixtures and additives for cement
between the organic and inorganic components. Following incorpora­ composites.
tion of the studied systems, it was found that the plasticity of the Lignin-based admixture Type of cement Effect of the Reference
resulting composite changed. The system with kraft lignin also improved admixture
the mechanical strength of the building material, although lignosulfo­ Unmodified and unfractionated lignin
nate did not produce any change in the value of this parameter [110]. Calcium lignosulfonate Wuyang Brand An increase in the [98]
In a further study, Klapiszewski et al. synthesized a kraft lignin–silica (CL) – part of a by- 42.5 R ordinary molecular weight of
product of sulfite Portland cement calcium
hybrid, and then used it as a concrete admixture to ascertain how it
pulping (Guangzhou (Guangzhou lignosulfonate
affected the physical and mechanical properties of the final cement Papermaking Co. Ltd., Cement Factory, increases the
composite [111]. The system was produced by mechanical milling, as in China) China) adsorption capacity
the previous work [110]. The synthesized kraft lignin–silica hybrid was on the surface of
considered a class I hybrid material, and the obtained systems differed in cement particles,
surface activity and
terms of the organic-to-mineral ratio, which amounted to 5:1, 2:1, 1:1, foam formation. CL
1:2 or 1:5 wt./wt., depending on the sample. The next stage involved of low or medium
adding these systems to the concrete mix in quantities of 0.5% or 1.0% molecular weights
wt. It was found that the kraft lignin–silica admixture improved the leads to the highest
values of surface
rheological and strength properties of the obtained cement composites.
charge of the
In the best configuration, using the lignin–SiO2 material in a 1:5 weight cement particles.
ratio, the strength improved by 40% relative to the reference mixture Dosage of CL to
and by 10–20% relative to a composite containing silica alone. More­ 0.5% wt. of the
over, combining lignin and silicon(IV) oxide in a hybrid material cement (molecular
weight of CL =
enabled improvement of the dispersion of the second cement compo­
10,000–30,000)
nent, which in turn led to improvement in its mechanical properties. results in maximum
Furthermore, mixtures containing the studied admixture had good fluidity in the
microstructural density and low pore content. It should be noted, cement paste.
Lignosulfonate No data The addition of [103]
however, that the lignin content in a hybrid system should not exceed
produced from 0.2% wt.
0.25% wt., since in such cases it most often reduces the concrete's alkaline lignin (AL) lignosulfonate from
compressive strength [111]. and enzymatic AL or EHR and
The idea of using lignin and its derivatives in various concrete ad­ hydrolysis residue commercial
mixtures and additives is motivated by, among others, the abundance of (EHR) obtained from lignosulfonate to
alkali-pretreated concrete increased
these substances, their relatively low cost and their distinctive proper­
bamboo residues. its compressive
ties, such as the ability to generate electrostatic interactions, the Commercial strength (after 28
occurrence of steric hindrance, and the ability to combine with inor­ lignosulfonate days) from 38.4
ganic compounds. (Shanghai Tingnuo MPa to 41.6, 42.6
Materials Co. Ltd., and 40.9 MPa,
Initially, lignosulfonates were used as concrete admixtures because
China) respectively.
of the possibility of direct application, as well as the fact that a positive Lignosulfonate from
impact on the composite could be obtained without any additional AL showed the best
chemical treatments. Among the methods discussed in this section, it performance in
appears that the method based on hybrid materials shows the most terms of improving
the fluidity of
promise. This approach, in the authors' view, will enable the design of an
cement paste
appropriate lignin-based hybrid system in the near future that may be compared with that
used as a relatively inexpensive functional additive to cement compos­ from EHR and the
ites; see Table 2. A comparison of the discussed methods is shown in commercial
product.
Fig. 5.
Sugar-reduced softwood Two types: CEM I The influence of [112]
calcium 52.5 N and CEM I SCL on the
3.2. Lignin-based rigid polyurethane foams lignosulfonate (SCL) 52.5 R (Cemex) ettringite formed in
(Borregaard) cement paste was
Another important application for lignin within the construction investigated.
Addition of SCL
industry is its use in the synthesis of rigid polyurethane foams (RPUFs). produced many
Polyurethanes are thermoplastic polymers with versatile uses, from small ettringite
thermal insulation to medical implants [117]. Polyurethane is a block crystals with cubic
copolymer consisting of low-molecular-weight blocks, i.e., polyesters or cuboidal shape
and length between
and polyethers covalently interlinked via urethane bonds (–NHCO–O–).
100 and 400 nm.
It is synthesized from three components: (1) polyisocyanate; (2) a These particles
polymer consisting of numerous hydroxyl groups; and (3) a chain caused an increase
extender. The second group contains polyester and polyether polyols. of SCL adsorption
The role of chain extender is performed by diols or diamines of lower by the cement
paste.
molecular weight (1,4-butanediol and 1,4-dibutylamine, respectively) Calcium, magnesium, CEM I Portland The impact of [113,114]
[13]. Polyurethanes can be found in many forms; however, foams are potassium or sodium cement with two various metal-
one of their most popular and frequently observed commercial appli­ lignosulfonates different C3A/ cation-containing
cations. Depending on their mechanical properties and density, they are CaSO4⋅2H2O and lignosulfonate-
C3A contents based plasticizers
classified as flexible, semi-rigid and rigid. The properties of poly­
on the properties of
urethane foams and their classification into the aforementioned groups cement composites
depend on the ratio between the so-called “hard” blocks that ensure (continued on next page)
material rigidity, and the “soft” blocks that are responsible for flexibility

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Table 2 (continued ) Table 2 (continued )

Lignin-based admixture Type of cement Effect of the Reference Lignin-based admixture Type of cement Effect of the Reference
admixture admixture

was studied. Lignin extracted from PO 42.5 R The degree of [102]

Depending on the pine wood with Portland cement sulfonation of the
parameters, each of formic acid and then (Shanshui Co., fractionated, then
these fractionated, oxidized China) oxidized and
lignosulfonates has and sulfomethylated sulfomethylated
a slightly or lignin was higher
moderately than that of the
different effect on unfractionated
the properties of lignin; therefore its
fresh cement, such workability,
as setting time, linearly correlated
viscosity, air with the degree of
content, water sulfonation of the
reduction, lignin samples, was
compressive also higher.
strength, water Lignopolymer – ASTM C150 Type Lignopolymer could [106]
permeability and polyacrylamide- I ordinary be an effective
workability. grafted kraft lignin Portland cement, superplasticizer for
Sugar-reduced softwood Two types: CEM I The addition of SCL [115] produced from alone and in a broad range of
calcium 52.5 N and CEM I immediately with BioChoice, a type of combination with high-surface-area
lignosulfonate (SCL) 52.5 R the mixing water, in kraft lignin (Domtar) two minerals: minerals (kaolin
contrast to delayed kaolin clay clay and
addition, increased (Sandersville, clinoptilolite
the specific surface USA) and zeolite) to be used
area. An increase in clinoptilolite in combination with
SCL content zeolite Portland cement.
reduced the yield (McKinney, USA), Lignopolymer has
stress and the each used as 25% significant effects
viscosity in most replacement for on the workability
systems, and cement by mass of these blends at 10
lengthened the times lower dosage
setting time. than commercial
admixtures.
Modified or fractionated and modified lignin
Soda lignin oxidized Two types: The alkali-O2 [107]
Oxidized and sulfonated Wuyang Brand MCL has higher [98]
with the alkali-O2 Megasementti oxidation method
calcium 42.5 R ordinary charge density
method. Pure soda CEM I 42.5 R for lignin with
lignosulfonate (MCL). Portland cement compared with CL,
lignin is Protobin (Finnsementti) moderately high
Unmodified calcium (Guangzhou and thus higher zeta
1000, a wheat straw and Plussementti dry solids proves to
lignosulfonate (CL) Cement Factory, potential, lower
soda lignin CEM II B-M (S-LL) be a promising
was part of a by- China) surface tension of
(GreenValue SA, 42.5 N method for the
product of sulfite solutions and larger
Switzerland) (Finnsementti) production of a bio-
pulping (Guangzhou adsorption
based concrete
Papermaking Co. Ltd., capability on
plasticizer. The
China) cement particles,
oxidized lignins
and it produces
were superior to
more hydrated
lignosulfonate and
ettringite needles in
showed good
the microstructure.
performance
MCL displays
comparable to
comparable fluidity
commercial
and compressive
superplasticizers.
strength to those of
Diethanolamine Cement clinker DML improved the [109]
formaldehyde
modified lignin (Lunan China cement's
condensates (the
(DML). Unmodified United Cement grindability and
gold standard for
lignin was obtained Company, China) particle size
water-reducer
from Gaotong distribution. DML-
materials).
Duoyuan Co. Ltd., modified cement
Oxidized and PO 42.5 R The fluidity of [99]
China mortars exhibited
sulfomethylated Portland cement cement with 0.3%
improved
sodium lignosulfonate (Shanshui Co., wt. dosage of MSL
mechanical
(MSL). Pure sodium China) can reach 185 mm,
properties. DML
lignosulfonate was which is
showed a very
obtained from alkali significantly higher
strong retarding
sulfite pulping (15%) than that
effect; the initial
(Tianhong Paper obtained with
and final setting
Industry Co. Ltd., unmodified sodium
times of cement
China) lignosulfonate. The
mortars containing
increase of
DML (0.04% wt.)
molecular weight
were increased by
and sulfo group
approx. 74.40% and
content after
47.90%,
modification
respectively.
improves the
Oxidized and Hydraulic cement Sulfomethylated [116]
performance of MSL
sulfomethylated kraft for general use, lignin has a higher
as a water reducer.
(continued on next page)

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P. Jędrzejczak et al. International Journal of Biological Macromolecules 187 (2021) 624–650

Table 2 (continued ) construction, as well as for transport and decoration [13]. The wide
Lignin-based admixture Type of cement Effect of the Reference range of possible applications of polyurethane results from the fact that
admixture it is a highly cross-linked polymer with a closed-pore structure, having
lignin. Softwood kraft type 10 (Target charge density, due
low thermal conductivity, high compressive strength, low density and
lignin was produced products Ltd., to which it adsorbs unique strength parameters, while maintaining a relatively small weight
using LignoForce™ Canada) better on cement [119].
(FPInnovations, particles, and the Substrates used to produce polyurethanes are obtained primarily
Canada). Commercial cement paste
from petroleum raw materials. These will be replaced by renewable
sodium lignosulfonate containing it has
was obtained from a better workability sources due to the development of modern biomass refining technolo­
local company than systems with gies, as well as the well-known challenges associated with these still
commercial widely available source materials, namely: (i) projected reduction in the
lignosulfonates and exploitation of fossil resources within the next two generations; (ii) the
softwood lignin.
Lignin as an organic component in hybrid systems
rapid increase in oil prices with no indications that it will drop signifi­
Kraft lignin–Al2O3 Portland CEM I The system [110] cantly; and (iii) increasing awareness of the need for sustainable
(KLA) and magnesium 42.5 R cement containing 0.5% wt. development [120].
lignosulfonate–Al2O3 (Górażdże Cement of lignin–Al2O3 The use of lignin is perfectly aligned with these trends. Furthermore,
(MLA) hybrid S.A., Poland) material is the most
owing to its random, non-crystalline structure, it can provide improved
materials. suitable for
Commercial kraft application as a compressive strength parameters and better thermal stability [121]. The
lignin (Sigma-Aldrich, cement mortar abundance of lignin and its natural renewal, as well as the fact that it is a
Germany), Vianplast admixture. The low-value by-product that is often produced in very large amounts, are
55 -commercial addition of hybrid also driving forces behind its use in polyurethane foam synthesis.
magnesium systems to cement
lignosulfonate mortars resulted in
Extracted lignin contains hydroxyl groups combined with aliphatic
(Biotech a favourable change chains, as well as aromatic rings, with both of these types of groups
Lignosulfonate of plasticity, while providing good reactivity with isocyanates [121]. Two approaches to
Handels GmBH, maintaining (MLA) the use of lignin in polyurethane synthesis are distinguished worldwide.
Austria) or even improving
The first method involves using lignin as a macromonomer for PU
the compressive
strength (KLA). polymer synthesis via cross-linking condensation. The second approach
Kraft lignin–SiO2 hybrid Portland CEM I Lignin–SiO2 hybrids [111] involves mixing lignin with a polyurethane matrix to create a lignin–PU
material. Commercial 42.5 R cement utilized as an composite, where lignin acts as a filler.
kraft lignin (Sigma- (Górażdże Cement admixture have a Most studies of polyurethane synthesis focus on the first approach,
Aldrich, Germany) S.A., Poland) favourable effect on
with three strategies distinguished in this regard: (1) direct use of lignin
rheological and
strength properties not subject to any prior modification, on its own or combined with other
of the cement paste. polyols; (2) use of lignin after fractioning in the presence of a solvent,
The combination of leading to a more homogeneous extract, with lignin also being activated
SiO2 and lignin
due to physical processing; (3) use of lignin after chemical modifica­
enabled good
dispersion of the tions, e.g. fragmentation, which increases solubility and the number of
silica in the cement hydroxyl groups, hydroxyalkylation or other functionalization, such as
paste. dealkylation, esterification, etherification and amination, which over­
come steric hindrances, increasing the availability of hydroxyl groups
and lignin reactivity [122,123]. An overview of this classification is
[118].
shown in Fig. 6.
This review discusses the uses of lignin in rigid polyurethane foams
Moving on to specific research, this chapter of the review will focus
(RPUFs), since these are used in structural materials for insulation and
primarily on applications of non-modified lignin. One of the first studies

Fig. 5. Methods of using lignin in admixtures and additives to cement composites and their advantages and disadvantages.

631
P. Jędrzejczak et al.
Fig. 6. Schematic division of lignin applications in polyurethane systems, reproduced with permission [123].
Copyright 2020, Elsevier.
to use non-modified lignin as an additive to polyurethanes was pub­
lished in 1988 by Feldman and Lacasse. It concentrated on kraft lignin,
combined with polyurethane-based putty in various weight ratios (the
kraft lignin content was varied from 0 to 20% wt.). It was found that
adding kraft lignin reduced the initial mixture setting time, although the
curing rate remained constant. The best tensile strength parameters
were exhibited by a putty with 5% wt. of kraft lignin. Moreover, the
durability of the putty did not deteriorate when kraft lignin was added
[124]. Another study concluded that lignin was involved in cross-linking
through some of its hydroxyl groups [125,126]. A key development for
the use of lignin in the production of rigid polyurethane foams was the
discovery that various types of lignin, namely kraft lignin, lignosulfo­
nates and hydrolytic lignin, were soluble in a number of polyethylene
glycols, over a wide range of molecular weights, from approximately 70
to 3000 g/mol. This enabled their use as a raw material in RPUF syn­
thesis without the need for prior processing. The aforementioned lignin
types are soluble in various polyols – diethylene glycol, triethylene
glycol and polypropylene glycol (PPG) – at temperatures of 60–70 ◦ C.
The process leads to the formation of lignin-containing polyol solutions
[127,128].
To obtain rigid polyurethane foams, Hatakeyama et al. mixed the
aforementioned mixtures containing 0–33% lignin with a plasticizer, a
surfactant (silicon oil) and a catalyst (dibutyltin dilaurate, DBTDL),
followed by MDI (poly(phenylene methylene) polyisocyanate), at room
temperature. This system was subjected to agitation, and a foaming
agent was added in the form of a small amount of water [127,128]. The
study concluded that polyurethane foam based on hydrolytic lignin and
obtained via the proposed procedure exhibited lower thermal conduc­
tivity, better physical properties and a price-to-performance ratio su­
perior to that of commercially available products [128].
In turn, Pan and Saddler estimated and compared the suitability of
kraft and organosolv lignin for replacing petroleum-derived polyols in
RPUF production. Fig. 7 shows representative polyurethane foams
containing both types of lignin. The brown color of these materials,
resulting from lignin content, is conspicuous, and the intensity of the
color is related to the type of additive used. Thus, dark-brown poly­
urethane foam is obtained by using a darker polymer derived through
the kraft process. This study also proved that lignin was incorporated
into the RPUF polymer network and not physically trapped in pores. The
research also concluded that PU foam density was reduced due to the
replacement of polyols by lignin; however, RPUF compressive strength
deteriorated with increasing lignin content, whether kraft or organosolv.
This resulted from the lower reactivity of lignin, caused by the fact that
its hydroxyl groups were less accessible, as well as its incomplete solu­
bility in polyol, which meant that it could not be uniformly dispersed in
the foam. Furthermore, adding lignin reduced the homogeneity of the
porous structure, and thus caused a deterioration of strength properties
[129].
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International Journal of Biological Macromolecules 187 (2021) 624–650
Fig. 7. Characteristic color of rigid polyurethane foams containing 50% hard­
wood ethanol organosolv lignin (HEL) (a), 50% hardwood kraft lignin (b) and
SEM of RPUFs: without lignin (c), as well as products with different HEL-to-
polyol molar ratio – HEL/P 25/75 (d), HEL/P 50/50 (e), HEL/P 60/40 (f),
HEL/P 70/30 (g), reproduced with permission [129]. Copyright 2013, Springer
Nature. Photograph of polyurethane foam made from organosolv lignin from
hardwoods after the oxypropylation reaction with propylene oxide (h), repro­
duced with permission [133].
Copyright 2005, Wiley-VCH.
Reducing the impact of lignin on the compressive strength of poly­
urethane foam requires measures to increase lignin's reactivity, namely,
to improve hydroxyl group availability, which is limited due to steric
hindrance. Improving the solubility of lignin in polyols can also be ex­
pected to have a positive effect on this parameter.
Kraft lignin not subjected to any chemical modification was also
found to have a positive effect when added to a nanocomposite
composed of wood and polyurethane (W-PU), with the first of the
components constituting 30% of the material weight [130]. Such a filler
was found to reduce the overall cost of a polyurethane foam, main­
taining or even improving some of its properties [131,132]. Lignin was
added into the reactive system as a partial substitute for the commercial
polyol diethylene glycol, replacing it at various weight ratios (0%, 5%,
10%, 15% and 20%). Lignin in such nanocomposites occurs in two
forms: as one of the polyols in the polymer part, and as one of the main
components of wood constituting the filler in the nanomaterial. Using
lignin as a polyhydric alcohol improves the compressive strength and
water-resistance of W-PU. It also increases its specific compressive
strength and compression modulus. A slight improvement in thermal
stability was also observed. The proposed method not only enables the
wide use of technical lignin, but is also a potential route for preparing
lightweight, rigid W-PU composites for use in construction, for example
[130].
The fractionation of lignin may be advantageous because the selec­
tion of an appropriate lignin fraction enables the obtaining of a
P. Jędrzejczak et al.
polyurethane material exhibiting specific features. For example, a low
NCO/OH ratio, i.e., the presence of numerous hydroxy groups in a
macromolecule relative to the amount of isocyanate, and low lignin
content (less than 20% wt.) usually lead to a soft and flexible product. In
contrast, hard and rigid PU materials can be obtained especially from
systems with high lignin content and a suitably high NCO/OH ratio
[123,134].
Wang et al. used sequential sedimentation to separate kraft lignin
into three groups, with high, medium and low molecular weight. Next,
each of these fractions was used in polyurethane synthesis. It was
concluded that using lignin with a higher molecular weight improved
the material's rigidity and strain resistance. The study also demonstrated
that the mechanical properties of PU can be controlled by selecting
appropriate lignin fractions [135].
The authors are not aware of any studies focusing on the use of
fractionated lignin without further modifications for synthesizing rigid
polyurethane foams. However, work in which lignin was first fraction­
ated, then modified and used for producing such materials is discussed
below. The advantages of fractionation itself were utilized in a study by
Griffini et al., where lignin after such treatment was used to synthesize
thermosetting polyurethane coatings. The resulting materials displayed
improved thermal stability, better ability to form a thin film, and
enhanced hydrophobicity. Thus, the obtained PU coatings produced
better adhesion to various substances, such as glass, wood, and metal
[136].
The preceding paragraphs have discussed the use of raw lignin or its
various fractions in PU synthesis. Let us now turn to lignin modification,
which enables an increase in the range of applications of lignin in this
area. The processes can be classified in two groups: (i) lignin fragmen­
tation or depolymerization resulting in oligomers; (ii) modification
involving the formation of new active sites, either to increase functional
group reactivity or due to a need to satisfy specific synthesis re­
quirements [123]. To overcome technical restrictions and those result­
ing from the polymeric nature of lignin, subjecting lignin to
oxypropylation is an ideal solution for the synthesis of rigid poly­
urethane foams. This process leads, among other things, to the freeing of
hydroxyl groups, especially those with hindered access due to links with
the aromatic ring and the macromolecule trapped inside, from steric and
electrostatic constraints.
Due to oxypropylation, solid-state lignin becomes a liquid polyol
mixture through the formation of numerous ether groups [137]. Wu and
Glasser were among the first to subject kraft lignin and lignosulfonates,
which are the two most frequent variants, to such modification [138].
Nadji et al. oxypropylated four other types of lignin: kraft, lignosulfo­
nates, organosolv, with the latter in both oxidized and non-oxidized
form. It was demonstrated that as a result of oxypropylation, the lig­
nosulfonates and organosolv could be efficiently used for producing a
viscous polyol mixture with properties similar to conventional com­
pounds used in RPUF synthesis, and the resulting foams exhibited good
thermal performance and dimensional stability [133].
In another study [139], modification was applied to kraft lignin
Fig. 8. Reaction diagram and illustrative structural formulas of used substrates and obtained products, MDI – 4,4′ -methylene diphenyl diisocyanate, reproduced with
permission [140].
Copyright 2020, Elsevier.
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International Journal of Biological Macromolecules 187 (2021) 624–650
obtained through pinewood pulping. It was then used to replace sucrose
and glycerol polyols at different ratios. Such mixtures were applied in
RPUF synthesis. It was concluded that it was possible to produce rigid
polyurethane foams from kraft lignin polyols without using any poly­
hydric alcohols or chain extenders in the synthesis, and the obtained
products offered better mechanical properties than their commercial
equivalents.
Other variants of lignin can be modified using propylene oxide,
including organosolv lignin. Li et al. subjected this type of lignin to
fractionation before oxypropylation, followed by RPUF synthesis [140].
A diagram of the reaction with propylene oxide and polyurethane syn­
thesis, as well as possible substrate and product structures, is shown in
Fig. 8. This study indicated that lignin fractions with lower relative
molecular weight and richer in hydroxyl groups combined with the
aliphatic chain led to rigid foams with lower density, higher compressive
strength and better thermal properties, compared with other lignin
fractions, including the reference sample. Furthermore, all of the rigid
polyurethane foams produced satisfied the requirements for insulating
materials, that is, their specific conductivity was in the range 0.02–0.05
W/(m⋅K) [140].
A team led by Cateto conducted a study that involved optimizing the
oxypropylation of lignins derived from three different pulping processes,
namely kraft, soda and organosolv, and different plant types, i.e.,
hardwood, softwood and non-wood, in terms of their application in
RPUF synthesis. The outcome of this method was the production of
polyhydric alcohols with values of viscosity and IOH (hydroxy index)
similar to those of commercial polyols used in RPUF manufacturing
[137]. Another study by Cateto et al. investigated the biodegradability
of these rigid polyurethane foams in an aqueous and constant environ­
ment under the action of five different fungi species. Tests showed that
the highest weight loss was experienced in the case of Phanerochate
chrysporium and Trametes versicolor strains that produce enzymatic ex­
tracts rich in lignin peroxidase, manganese peroxidase and laccase.
These are three enzymes that, when combined, effectively contribute to
lignin decomposition. Furthermore, it was observed that the presence of
an additional food source in the form of polyol produced not only from
lignin, but also sorbitol in this case, promoted biodegradation [141].
Scientists are also looking for new solutions where lignin dissolves in
the most optimal conditions and to the highest degree, in order to in­
crease the extent of replacement of petroleum-derived polyols in the
production of rigid polyurethane foams. An example of such a mixture is
a ternary, deep eutectic solvent prepared from choline chloride, glycerol
and polyethylene glycol 400, in which lignin obtained through enzy­
matic hydrolysis best dissolves at a temperature of approximately 60 ◦ C.
The obtained lignin enables the replacement of as much as 58.6% wt. of
commercial polyols in rigid polyurethane foams, while maintaining
good mechanical properties. This value is one of the highest in terms of
the effective use of lignin in RPUFs. Nonetheless, when lignin accounts
for 10–30% of all polyols, the obtained polyurethane foams exhibit the
most uniform pores and highest compressive strength [142].
Summing up the applications of lignin in the synthesis of rigid
P. Jędrzejczak et al.
polyurethane foams that can be further effectively used in construction,
e.g., for insulation, it is seen that this is an encouraging approach to the
valorization of waste materials. This is evidenced by the attention the
topic is receiving in terms of the yearly numbers of related publications,
patent filings and citations. The great advantage of methods incorpo­
rating non-modified lignins into RPUFs is their cost-effectiveness,
although a disadvantage is certainly the low amount of replaced
petroleum-derived polyhydric alcohols in polyurethane foam synthesis.
As far as modified lignins are concerned, each subsequent treatment
reduces the economic benefit of such an application. Furthermore,
modifiers, besides increasing the cost of such an approach, are often
made from fossil fuels, which in turn result in greater environmental
impact than in the case of direct use of commercial polyols. Neverthe­
less, modifications enable the replacement of a greater amount of
petroleum-derived polyhydric alcohols and the production of more rigid
polyurethane foams with favourable performance. Table 3 contains
summary information on the use of lignin in RPUF synthesis.
3.3. Lignin as a corrosion inhibitor and protective coating
The greatest disadvantage of current commercial corrosion in­
hibitors is toxicity. Thus, they must be replaced by natural substances
that are safe for the environment and human health [167]. Lignin, which
exhibits antioxidant properties [168], is potentially an ideal corrosion
inhibitor. However, features that limit the application of lignin for this
purpose include its high inhomogeneity and structural complexity, as
well as its high distribution of molecular weight. Still, these issues can be
overcome through modification and fractionation of lignin [169,170].
Work by Hussin et al. has verified that three lignin types, namely
kraft, soda and organosolv, are natural corrosion inhibitors for mild steel
under acidic conditions. In their study, all types of lignin were frac­
tionated using the ultrafiltration process, and then assessed in terms of
anti-corrosion applications. Electrochemical impedance spectroscopy
(EIS) results indicated that adding each of the analyzed lignin types
improved the corrosion inhibition ability of the resulting protective
coatings. The authors attribute this to the fact that the presence of lignin
increases the surface resistivity of mild steel [169].
It was also found that the rate of corrosion of mild steel in an acidic
environment decreased in samples coated with lignin particles. Here, the
soda variant, in a 500 ppm concentration, exhibited the highest corro­
sion inhibiting efficiency. For other lignin types also, the best corrosion
inhibiting properties were found in the case of the highest concentration
(500 ppm). In addition, the potentiodynamic polarization research
technique provided information that ultrafiltered lignin reduced corro­
sion current density. This was found to be due to the inhibitor being
adsorbed at the mild steel/acid solution interface [169].
Another study focused on selected lignin-based monomers: p-cou­
maric acid, ferulic acid and hydroxybenzaldehyde. It was found that all
of the obtained substances inhibited mild steel corrosion in an envi­
ronment with a pH of approximately 7. Synergistic interactions between
these three monomers, with significant impact on the rate of the
aforementioned degradation process, were also reported in this study
[171].
In work by Najarro et al., a copolymer consisting of a kraft lignin core
and aliphatic polyester oligomers (with degree of polymerization DP <
25), i.e., ε-caprolactone, was synthesized. The lignin–ε-caprolactone was
created using ε-caprolactone ring-opening polymerization with lig­
nin–OH as a macroinitiator and tin(II) octanoate as a catalyst. An
attempt was also made to control the length of polyester oligomer chains
embedded in the lignin. Appropriate thermo-setting properties, excel­
lent film-forming abilities and outstanding adhesion to a stainless steel
substrate were found in the case of a copolymer containing short oli­
goesters with DP < 5 [172]. In addition, lignin can be used as a carbon
source for producing heat-swelling paint, which insulates steel struc­
tures in the event of fire and increases their safety level. Such material
also contained (besides lignin) polyaniline, ammonium polyphosphate
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International Journal of Biological Macromolecules 187 (2021) 624–650
and expandable graphite. Lignin is a good substitute for non-renewable
substances, without compromising fire protection properties. In the case
of a sample with HCl-doped polyaniline, the flame retardant properties
were improved further. A coating containing 10% wt. of lignin and 10%
wt. of HCl-doped polyaniline exhibited the best efficiency [173].
Another study used kraft and organosolv lignin to produce anti-
corrosive coatings for phosphate steel. These variants of lignin were
dissolved in one of six available organic solvents: (1) butyl acetate, (2) 2-
propanol, (3) 1-methoxy-2-propyl acetate, (4) 1-methoxy-2-propanol,
(5) diethylene glycol monobutyl ether, and (6) 1-butanol, in order to
compare their efficiency with dimethyl sulfoxide, and hence to select the
most appropriate solvent for further studies. Good solubility in systems
containing the fourth or fifth of the aforementioned compounds was
observed in the case of both lignin types. Moreover, the organosolv
variant was found to dissolve well in 1-methoxy-2-propyl acetate. Next,
highly concentrated lignin solutions (100 g/L) without insoluble resi­
dues were sprayed onto a cleaned phosphate steel substrate. It was
demonstrated that the coating based on kraft lignin dissolved in 1-
methoxy-2-propanol had the ability to reduce phosphate steel current
density by more than two orders of magnitude, in addition to increasing
charge transfer resistance. However, the resulting layer was unable to
provide long-term anti-corrosion protection in aggressive conditions
[174]. Besides the aforementioned work, there are also a number of
publications reporting on the use of lignin or its derivatives for protec­
tion against corrosion, for instance by the formation of functional
coatings [175]. Uses of lignin and its derivatives as corrosion inhibitors
for construction applications are summarized in Table 4.
Belgacem et al. used organosolv lignin as a filler in inks, varnishes
and paints. This was achieved by adding lignin to the referenced prod­
ucts and thoroughly mixing them. The phenomenon of misting, which is
defined and measured as a weight percentage of emissions to the at­
mosphere when the material is transferred onto another surface, at a
specified rate, is important in the paint, varnishes and printing in­
dustries. The addition of organosolv lignin to a coating substance re­
duces this issue [185]. Furthermore, it was concluded that the phenolic
OH groups were responsible for an increase in the elastic nature of the
paints, which led to reduced misting. Disadvantages of lignin as a paint
filler include, among others, the fact that it gives them a brown tint
[185].
Lignin has also been used to coat cellulose nanocrystals. The
resulting product was found to be useful as a substrate for obtaining a
superhydrophobic coating when applied to a wooden surface [186].
Furthermore, An et al. utilized lignin/polycaprolactone nanofiber
membranes for the production of a porous mesh to protect wood from
mold, which is detrimental to human health [187].
Huang et al. produced ligno-cellulose nanofibrils (LCNFs) with a high
lignin content of 25.59% according to the Klason test, obtained from
bark. They can be used as a modifier for water-based acrylic varnishes,
which are among the most commonly used paints for furniture, interior
decoration, buildings, murals, etc. Synthesized coatings were applied to
protect spruce (Picea abies) and sugar maple (Acer saccharum) wood.
LCNFs were mixed with both an acrylic primer and a finishing paint.
Introducing this material into coatings was found to improve their
hardness and abrasion resistance. What is more, a modified coating
exhibited markedly improved aging resistance [188].
In recent years, lignin-based nanomaterials, e.g. uniform colloidal
nanospheres from lignin, have been widely designed and manufactured,
and attempts have been made to use them in coatings and resins
[189,190]. Lignin is also used in sunscreen and UV-blocker, due to its
ability to absorb UV light and its antioxidant properties, and has the
potential to be used in external coatings, paints and other such materials
[191–196].
In summary, lignin and its derivatives are being utilized to produce
new, more sustainable corrosion inhibitors and protective coatings. The
obtained materials are not only more environmentally friendly and
sustainable, but critically, their properties are comparable or superior to
P. Jędrzejczak et al. International Journal of Biological Macromolecules 187 (2021) 624–650

Table 3
Overview of lignin for the synthesis of rigid polyurethane foams (RPUFs).
No. Lignin type Lignin application/methodology Result Reference

1. Kraft lignin (Sigma Company)
2. Hydrolytic enzymatic lignin isolated from
cellulolytic enzyme hydrolysis of corncob
(Longlive Biological Technology Co Ltd., China)
3. BioChoice Lignin, a commercial kraft lignin
(Domtar, USA)
4. ALCELL lignin, a hardwood organosolv lignin
5. Indulin AT, a commercial kraft lignin (Ingevity
Corporation, USA)
6. Indulin AT, a kraft lignin (Ingevity, USA)
7 Lignin extracted from forestry and non-food
agricultural materials using bacteria and yeast
for bioethanol production (Mascoma
Corporation, Canada)
9 Kraft lignin (370959 from Sigma-Aldrich)
10 Commercial softwood kraft lignin
11 Pine kraft lignin (Sigma-Aldrich, Poland)
12
Lignin was subjected to liquefaction and then, as a
polyol mixture, was agitated with other polyhydric
alcohols and other substrates, including silicon
dioxide particles, to produce a rigid polyurethane
foam containing the aforementioned oxide.
Triple, deep eutectic solvents are designed to
effectively dissolve lignin under relatively mild
reaction conditions. The obtained products were
used to partially replace commercial polyols in the
production of rigid polyurethane foams containing
lignin.
Lignin was used to synthesize non-toxic and non-
isocyanate polyurethane foams (NIPUs) via
oxyalkylation with glycerol carbonate.
Polyalcohols produced as a result of organosolv
lignin oxypropylation were used as a substitute for
10% to 30% of petrochemical polyhydric alcohols,
to produce rigid polyurethane foams.
Kraft lignin was oxyalkylated with ethylene
carbonate to synthesize polyhydric alcohols,
followed by their use in the process of producing
rigid polyurethane foams.
Lignin surfaces were functionalized with
polyisocyanate through a prepolymerization
treatment and used in the synthesis of rigid
polyurethane foams.
This is a mixture of polyols derived from lignin and
soybean oil used to obtain biodegradable, rigid
polyurethane foams. Lignin content accounted for
0 to 25% of the total amount of polyhydric alcohols.
Lignin was dispersed in polyether polyol, at a
temperature of approximately 120 ◦ C, close to kraft
lignin's “softening” point, in order to improve its
dissolution, disaggregation and dispersion. Glycerol
acts as a cross-linking agent and compatibilizer.
Lignin was used to synthesize rigid polyurethane
foams.
Kraft lignin was surface functionalized using pMDI,
a polyisocyanate based on methyldiphenyl
diisocyanate. The reaction between pMDI
isocyanate groups and lignin hydroxy groups
resulted in urethane groups, which lead to improved
phase compatibility when lignin is mixed with
polyol during RPUF synthesis. The modified lignin
was used to replace 0–40% of conventional,
petroleum-derived polyols.
Lignin was subjected to liquefaction in a process
supported with microwaves, using pure glycerol and
1,4-butanediol, to obtain polyols. The polyols were
then used to produce rigid polyurethane foams,
where they replaced 25% or 50% of petroleum-
derived polyhydric alcohols, depending on the
sample.
Adding silicon dioxide nanoparticles led to [143]
decreased foam pore size from 1500 μm to 300 μm.
The open pore content and RPUF density were also
reduced. Adding SiO2 improved the thermal
stability and reduced the glass transition
temperature. On the other hand, the compressive
strength was diminished.
The lignin-based rigid polyurethane foams [142]
exhibited lower elastic modulus and higher
compressive stress (at 10% compressive strain the
compressive strength of all samples containing
lignin exceeded 356 kPa) and a high degree of
lignin replacement, which amounted to 58.6% in
the most favourable case; to the best knowledge of
the authors, this is the maximum value meeting
RPUF standards.
This process produces polyurethanes consisting of [144]
100% bio‑carbon. The application of catalytic
cyclic carbonization led to NIPUs with properties
comparable to diisocyanate-based polyurethanes.
Adding polyols derived from organosolv lignin to [145]
polyurethane systems improved their reactivity.
Apparent density was also reduced due to the
incorporation of lignin into RPUF synthesis.
Synthesized RPUFs met the standards for insulation
applications in terms of brittleness and dimensional
stability.
The described innovative oxyalkylation method [146]
with ethylene carbonate enabled conversion of
kraft lignin into biopolyols with more than 80% of
OH groups linked via an aliphatic chain.
Surface functionalization of lignin improved its [147]
effectiveness as a reactive cross-linking filler. The
addition of this modified kraft lignin to RPUFs
improved their thermal stability and mechanical
performance, without negatively affecting
insulating properties and water absorption.
The resultant rigid polyurethane foams were [148]
biodegradable and produced from 100% polyols
based on bio-resources. All obtained RPUFs
exhibited similar internal morphology and cellular
microstructure. Lignin particles were found to react
with polyisocyanate through active –H and –CNO
groups, which leads to the formation of a three-
dimensional macromolecule with improved
mechanical, thermal and biodegradability
properties. This process gives the foam self-grow
ability, while saving time and being cost effective.
The method enabled effective incorporation of 10% [149]
wt. of kraft lignin into a mixture of polyols. Owing
to the better dissolution, disaggregation and
dispersion, it was possible to obtain RPUFs with
thermal insulation improved by 5% and
compressive strength enhanced by 4%, compared
to a lignin-free reference sample.
RPUFs containing up to 30% of surface- [150]
functionalized lignin exhibited thermal and
mechanical properties comparable to conventional
RPUFs. In comparison with foams with non-
modified lignin, the specific compressive strength
was higher by 47%, and the modulus of elasticity by
45%. Based on life cycle assessment (LCA), it was
concluded that the environmental impact was
lower. The described method is an interesting
strategy for producing RPUFs with high lignin
content for structural applications.
A biopolyol containing 15% lignin and produced at [151]
a temperature of 150 ◦ C exhibited the most optimal
parameters, which make it suitable for RPUF
production. The obtained rigid polyurethane foams
are characterized by greater apparent density,
compressive strength and thermal stability.
[152]
(continued on next page)

635
P. Jędrzejczak et al.
Table 3 (continued )
No. Lignin type
Lignin from “lignin-first biorefinery”. Lignin was
obtained from apple wood (hardwood)
13 Kraft lignin precipitated from black liquor
leftover of eucalyptus kraft pulp production
(Suzano Celulose e Papel, Brazil)
14 Hydrolytic lignin, a residue of sugar/ethanol
production from Aspen wood (FPInnovations)
15 Alkaline lignin (Chuangzhou Peaks Chemical)
16 Sodium lignosulfonate (Borregaard LignoTech,
USA)
17 Hydrolytic lignin, a by-product of a proprietary
hardwood fractionation process for bioproducts
– TMP bio-process (FPInnovations)
18 Kraft lignin, produced using the proprietary
LignoForce process (FPInnovations, Canada)
19 Calcium lignosulfonate (Xinyi Feihuang
Chemical Co. Ltd.)
International Journal of Biological Macromolecules 187 (2021) 624–650
Lignin application/methodology
Apple tree (hardwood) was subjected to catalytical
depolymerization with Ru/SiC or Ru/C as catalysts.
The obtained mixture was filtered to obtain liquid
and solid phases. The former phase was extracted
using hexane, to obtain monomeric (extract) and
dimer/oligomer-rich (residue) phases. These
residues were then mixed, at different weight ratios
(0%, 10% or 50%) with polyether polyol and heated
at 110 ◦ C. The obtained systems were used in the
synthesis of rigid polyurethane foams.
Kraft lignin was incorporated into a structure of
rigid polyurethane foams by the free-pour method.
Biopolyols for RPUF production consisted of a
mixture of castor oil and crude glycerine, where the
kraft lignin particles acted as a filler (in contents of
1%, 5% and 10% wt. relative to total weight).
Lignin was liquefied/depolymerized using a 50/50
water–ethanol mixture. This stage was followed by
oxypropylation of lignin to obtain liquid polyols,
which have high bio-compound content. This
process was conducted within a reactive system
containing lignin, propylene oxide, potassium
glycerolate and acetone. A mixture of polyhydric
alcohols was used to create rigid polyurethane
foams via the one-shot method.
To make alkaline lignin suitable for use in
polyurethane foam synthesis, it was liquefied in a
mixture of polyethylene glycol 400 and glycerol in a
4:1 weight ratio. The product was used for
synthesizing polyurethane foams via the one-pot
method, where it replaced 0%, 25%, 50%, 75% or
100% of commercial polyether polyols.
Two types of lignin, non-modified and subjected to
alkaline hydrolysis, were used for the production of
polyurethane foams. RPUFs were synthesized using
the one-pot method, by mixing lignin with polyols
(polypropylene glycol and/or glycerol), water,
catalyst and a surfactant. Polyisocyanate was added
only in the next step. When it reacts with OH groups,
it creates urethane groups and produces
polyurethane.
Hydrolytic lignin was subjected to depolymerization
without a catalyst or in the presence of H2SO4 or
NaOH as reaction catalysts. Two different solvents
were used: water, and a 1:1 v/v water–ethanol
mixture.
The kraft variety of lignin was subjected to
hydrolytic depolymerization. Sodium hydroxide
and distilled water were used for this purpose.
H2SO4 was used in the lignin precipitation process.
The depolymerized kraft lignin had a high biological
compound content of 50% wt. The product was then
oxypropylated using propylene oxide. The system
also contained a mixture of glycerol and KOH. The
one-shot method was employed for RPUF synthesis,
with the depolymerized kraft lignin used to partially
replace polypropylene glycol 400 or sucrase polyols,
or with the oxypropylated kraft lignin fully
replacing those substances.
The first stage involved dissolving lignin in a
mixture of glycerol and diethylene glycol (80:20
weight ratio) in the presence of a catalyst. The
resultant polyols were used to partially replace
petroleum equivalents in the synthesis of rigid
polyurethane foams. To improve the flame-
retardant properties of the foams, commercial
flame-retardant polyol was added to the reaction
636
Result Reference
SiC was shown to be an effective and regenerable
catalyst carrier in lignin biorefining. The partial
replacement of petroleum-derived polyols with
hexane extraction residues in RPUF production
maintains the uniform cellular structure and
density of the materials, and improves their water-
repellent and fire-retardant properties.
The obtained composite foams exhibited higher [131]
linear cellular density and lower pore diameter,
with the changes becoming more evident with
increased lignin content. The application of lignin
as a filler impacted RPUF mechanical properties
relatively well. The resultant foams satisfied the
minimum compressive strength value of 65 kPa
required for their application as cores in structural
panels.
The obtained polyols used for RPUF production had [153]
bio-compound contents in the range 50–70% wt.
The physical, mechanical and chemical properties
of the produced foams strongly depended on the
bio-content of the polyols and the amount of the
physical blowing agent. The obtained RPUFs
exhibited high compressive strength (120–1151
kPa) and low thermal conductivity (0.029–0.034
W/(m⋅K)). Furthermore, they were thermally stable
up to approximately 200 ◦ C and their pores were
closed. These features make the foams suitable for
use as insulating and structural materials.
Polyurethane foams with more than 50% lignin- [154]
based polyether polyols were used to obtain RPUFs
with a density of ≥55 kg/m3 and a compressive
strength of ≥0.3 MPa.
Rigid polyurethane foams were obtained only from [155]
two mixtures, without glycerol and hydrolyzed
lignin. Lignosulfonate accounted for 100% of the
polyols in the first sample and 30% in the second,
the remaining 70% polyhydric alcohols being
polypropylene glycol. The values of Young's
modulus for the rigid foams were 4.42 MPa and
3.81 MPa, respectively.
The obtained depolymerized hydrolytic lignin has [156]
an aliphatic hydroxy group value of approx. 227.1
mg KOH/g, and a total hydroxyl value of 442.0 mg
KOH/g, making this product suitable for
synthesizing rigid polyurethane foams. For this
application, the system without a catalyst using a
water–ethanol mixture as a solvent was deemed the
most advantageous.
The synthesis enabled the obtaining of bio-based [157]
rigid polyurethane foams using depolymerized
kraft lignin with a bio-content of 50% wt. All
synthesized RPUFs exhibited good compressive
strength (216–515 kPa at 10% compressive strain)
and thermal conductivity in the range 0.029–0.040
W/(m⋅K). In the case of oxypropylated lignin, it was
possible to obtain rigid polyurethane foams with an
excellent set of physical, mechanical and thermal
features. In the light of the above, it was suggested
that the synthesized RPUFs could be used for
insulation.
The process led to a rigid polyurethane foam [158]
nanocomposite with significantly enhanced
mechanical properties, thermal efficiency, fire
resistance and fire behavior. Compared to the foam
obtained using only commercial polyether polyol,
the specific compressive resistance was increased
by approximately 10%. Moreover, the limit oxygen
index increased in the case of the modified RPUF
(continued on next page)
P. Jędrzejczak et al.
Table 3 (continued )
No. Lignin type
20 Alkaline lignin extracted from corncob residue
after hydrolysis of hemicelluloses (Longlive
Biological Technology Co., China)
21 Alkaline lignin extracted from corncob residue
after hydrolysis of hemicelluloses (Longlive
Biological Technology Co., China)
22 Sodium lignosulfonate (Jiahe Wood Technology
Co. Ltd., China), raw lignin derived from the
enzymatic decomposition of corn straw in
ethanol production (Songyuan Chemical Co.
Ltd., China)
23 Vanillex N and Vanillex HW, commercial sodium
lignosulfonates (Nippon Paper Chemicals Co.,
Japan)
24 Wheat straw alkaline lignin (Shandong Quanlin
Paper Co. Ltd., China)
25 Lignin extracted from non-food agricultural and
forestry materials by using yeast and bacteria to
produce bioethanol (Mascoma Corporation)
26 Indulin AT, a softwood lignin, obtained by the
kraft pulping process (MeadWestvaco, USA).
Alcell lignin extracted from mixed hardwoods
International Journal of Biological Macromolecules 187 (2021) 624–650
Lignin application/methodology
system. The additive was used in combination with
polyurethane, microencapsulated ammonium
polyphosphate and organically modified layered
double hydroxide.
A 4:1 mixture of polyethylene glycol 400 and
glycerol was used in melting of alkaline lignin in a
process catalyzed with sulfuric(VI) acid and heated
with microwave radiation. Next, polyurethane
foams were synthesized using the one-shot method.
Unmodified lignin was used to replace polyols in the
production of rigid polyurethane foams by the one-
shot method. Lignin and polyhydric alcohol
contents were determined using various molar ratios
between hydroxyl groups found on lignin and
present in the other compound (1:9, 2:8, 3:7, 4:6 and
5:5). In addition, pulp fibers were used for
reinforcement.
The first stage in the production of a lignin-based
phosphate melamine compound (LPMC) is the
pulping of both lignin varieties in a mixture of
polyethylene glycol 400 and glycerol, with sulfuric
(VI) acid as a catalyst. Anhydrous aluminum
chloride and preheated polyphosphoric acid were
then added to the set-up for the purpose of
esterification. The next stage involved pouring
melanin, previously dissolved in ethanol, into the
reactor. Each stage ended with heating the system
up to 160 ◦ C, constantly mixing and purging with
nitrogen. Subsequently, the produced LPMC was
used to partially replace (5%, 10%, 15%, 20%)
polyethylene glycol 400 as a polyol in polyurethane
synthesis, following the one-shot method.
Two types of pure lignosulfonates, acidic and basic,
were dissolved in three different polyols –
diethylene glycol, triethylene glycol and
polyethylene glycol 200 – at a polymer-to-solvent
ratio of 1:4. Both obtained lignosulfonates were then
mixed together in different ratios and used for
polyurethane synthesis.
Initially, lignin was subjected to
hydroxypropylation. For this purpose, it was first
dissolved in a 0.06 M aqueous NaOH solution, and
then formaldehyde was added to the set-up. The
next stage involved acidifying the obtained product
with HCl to precipitate lignin; the sediment was then
centrifuged. The synthesized product was
subsequently placed in chloroform, which also
contained triethylamine. After reaching a
temperature of 60 ◦ C, a chloroform POCl3 solution
was dropped in. After the reaction, ethylene glycol
and another chloroform batch were added to the
system. The synthesis led to the formation of
lignin–POH with –OPO(OCH2CH2)2 groups. This
was followed by preparation of a micro-
encapsulated phenolic-coated ammonium
polyphosphate (PFAPP), which is a flame retardant
agent. Ultimately, both the functionalized lignin,
used to partially replace commercial polyols, and
PFAPP were employed to synthesize rigid PU foams
using the one-shot and free-rise methods.
Lignin was used in the synthesis of rigid
polyurethane foams, as a reactive reinforcing filler.
A polyol soybean oil derivative was used in the
synthesis of RPUFs to replace 50% wt. of its
petrochemical substitute. The one-shot and free-rise
methods were employed to synthesize polyurethane
foams. Lignin content varied depending on the
sample and amounted to 0%, 5%, 10% or 15% wt.
relative to the total polyol weight.
Both lignin types were used to replace commercial
polyols in RPUF synthesis. The first stage involved
oxypropylating lignins to obtain polyols. They were
637
Result Reference
from 19.0% to 28.1%, a value proving the ability to
spontaneously extinguish fire.
The use of microwave radiation made it possible to [159]
optimize polyol production using molten lignin.
The efficiency of the first stage was high and
amounted to 97%, and the obtained polyhydric
alcohols had a hydroxyl value that was sufficient
for their application in the synthesis of rigid
polyurethane foams.
The application of pulp fibers enabled the obtaining [160]
of RPUFs with greater pore regularity and lower
density. The change in these properties positively
affected thermal conductivity. Introducing the
fibers does not weaken the compressive strength of
RPUFs. Furthermore, it improves their thermal
stability.
A lignin-based phosphate–melanin compound was [161]
successfully synthesized by inoculating groups with
phosphorus and nitrogen onto lignin. Using LPMC
as a substitute for commercial polyols in
polyurethane foam synthesis also had a positive
outcome. It was observed that if the content of this
compound did not exceed 15%, its impact on PU
morphology and mechanical properties was
negligible. Compared to pure polyurethane, a
sample with 15% of LPMC exhibited twice the
compressive strength, excellent thermal stability,
the ability to form carbonization residues, self-
extinguishing properties, and inhibition of melt-
dripping and smoke generation. This contributes to
the generation of non-flammable smoke and a layer
protecting the deeper located polymer during
polyurethane degradation resulting from heat flux.
The synthesis showed that it was possible to [162]
produce rigid polyurethane foams with properties
suitable for specific practical applications.
As a result of lignin modification, which involved [163]
implanting a phosphorus-containing compound
into the structure, the researchers successfully
obtained a functionalized lignin. The resultant
polyurethane foam, also containing PFAPP, had
lower pore size and greater homogeneity. Using
modified lignin also resulted in increased RPUF
density and compressive strength. Owing to the
high degree of cross-linking, the damping
properties and the storage modulus significantly
increased. The initial decomposition temperature
and carbonization residues improved as a result of
incorporation into a PFAPP structure. The obtained
RPUFs also exhibited improved thermal stability.
Adding PFAPP efficiently reduced foam
flammability, while partial replacement of
commercial polyol with functionalized lignin led to
a decreased or unchanged oxygen index value.
Adding lignin to act as a reactive filler led to a foam [164]
with more uniform overall cell structure, thinner
cell walls and a higher number of damaged cells.
The FTIR study indicated covalent bonds between
lignin molecules and the foam. Adding lignin was
also beneficial in terms of RPUF mechanical and
thermal properties.
The results showed that using lignin-derived [165]
polyols, which led to a lignin content in target
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P. Jędrzejczak et al. International Journal of Biological Macromolecules 187 (2021) 624–650

Table 3 (continued )
No. Lignin type Lignin application/methodology Result Reference

(maple, birch, and poplar) by an organosolv
process using aqueous ethanol (Repap
Enterprises Inc., USA)
27 Ethanol organosolv lignin extracted in a toluene-
ethanol mixture (2:1 v/v) from pine wood chips
then used to synthesize rigid polyurethane foams by
the free-rise method. The foams were tested for
biodegradability in the presence of Aspergillus niger.
Organosolv lignin was oxypropylated to obtain
polyhydric alcohols, by mixing with propylene
oxide and potassium hydroxide as a catalyst, and
gradually increasing the pressure and temperature.
The obtained polyols were then employed to
synthesize rigid polyurethane foams, using the one-
shot method. The RPUFs were additionally
reinforced with cellulose nanowhiskers (CNWs)
(0.1% and 5% wt.).
RPUFs in the range 10–12%, increased
polyurethane biodegradability.
Increased CNW content from 0 to 5% wt. results in a [166]
decrease in average pore size from 320 ± 20 to 191
± 16 μm. The density of the foams also increases
with cellulose nanowhisker content, and only when
this value is 5% does it fail to satisfy the
requirements for thermoinsulating materials in the
construction industry, i.e., it exceeds the range
30–45 kg/m3. The obtained rigid polyurethane
foams have compressive strength exceeding 200
kPa, which is a value suitable for most applications.
In the case of addition of 5% wt. of CNWs, this
increases to 520 kPa. The thermal properties of
RPUFs were also improved.

those of their crude oil-based equivalents currently available on the
market.
3.4. Lignin as a precursor material for resins
Lignins are also used to synthesize phenol–formaldehyde resins
(PFRs). These polymers are synthesized mainly from petroleum-derived
phenols and formaldehyde. Phenol resins, owing to their good me­
chanical properties, flexibility, low price, high thermal stability, and
resistance to fire, water and chemical substances, have multiple appli­
cations, for example, in the aviation industry, as binders in chipboards,
in the production of insulating foams, paints and coatings, as well as in
the electrical and lighting industry [197–199]. Considerable efforts to
partially or fully replace the previously used petroleum-derived raw
materials have been undertaken in recent years in relation to PFR syn­
thesis. Three main motivations for this change are distinguished,
namely: (1) the increasing need to use more sustainable biological raw
materials, mainly due to the depletion of non-renewable crude oil re­
sources resulting in its increasing price, as well as progressing climate
change; (2) the need to improve the health and safety of consumer
product manufacturing; (3) the goal of improving the performance of
resins [197]. With regard to the first of these motivations, the attention
of many scientists is focused on using biomass as a renewable source of
organic reagents, which can be used for the synthesis of phenyl­
–formaldehyde resins. This is largely due to the rapid development of
chemical technology over recent decades. This progress has enabled the
easy conversion of biomass into valuable chemical substances and bio­
fuels [197,200]. The main raw material in the synthesis of bio-materials
is lignocellulose, used to make, among others, phenol compounds, al­
cohols, and furan-based substances in the course of biorefining. A po­
tential ecological counterpart of phenols, which serve as a substrate in
the phenol resin synthesis reaction, is lignin, which is one of the main
components of ligno-cellulose biomass. Lignin owes this application to
its aromatic structure, substituted with numerous hydroxyl groups, and
is currently widely used in PFR production. Furthermore, lignin is
recognized as a product far less harmful to health, both in the course of
synthesis and during use of phenol resins, than phenol, which is classi­
fied by the European Chemical Agency as a mutagenic, carcinogenic and
toxic compound [197,201]. Phenol resins modified with one of the
lignin variants containing sulfur, i.e., kraft lignin or lignosulfonates,
exhibit reduced mechanical properties. This is caused by the lower
reactivity of these lignin types with formaldehyde, compared to phenols
[197]. In their work, Park et al. had organosolv lignin partially replace
phenol in phenol–formaldehyde resins used as coatings. Organosolv
lignin was first acetylated, and then hydroxy-methylated to increase its
reactivity. The lignin content in the obtained resins used to produce
coatings and applied on a cardboard substrate was 30% wt. The applied
layer provides the protected surface with water-repellent properties,
although the contact angle is lower [202]. Yet another study [203]
verified the thermal degradation of phenol–formaldehyde resins con­
taining lignin. Klapiszewski et al. published works concerning the use of
lignin and its derivatives in phenol resins. These studies focused on: (i)
the use of functional hybrid lignin–SiO2 materials in the production of
phenol–formaldehyde resins with a potential application as binders in
abrasives [204]; (ii) the possibility of using calcium lignosulfonate as an
eco-friendly additive to cross-linked composites based on phe­
nol–formaldehyde resins [205]; (iii) activation of magnesium lignosul­
fonate and kraft lignin using various oxidizing agents, with a view to
their application in phenol resin composites which were then used to
produce abrasive elements [206]. Despite the work briefly described
above, very few scientists have so far focused on the introduction of
lignin into phenol–formaldehyde resins, in the context of creating
functional coatings. One of the main applications for these products is in
the wood product industry, as a binder in the production of chipboards,
plywood, fiberboards, MDF boards, etc. [207].
Kalami et al. used non-modified lignin as a by-product of corn straw-
based cellulosic bioethanol production, which involves pre-treatment
with dilute acid and enzymatic hydrolysis, to replace 100% of phenol
in a phenol–formaldehyde resin. Replacing the entire content of phenol
will not only lead to a more sustainable product based on a renewable
raw material, but will also benefit human health. The obtained resin,
containing 100% lignin and phenol resorcinol formaldehyde adhesive, is
used in the production of OSB boards, and the plywood exhibits similar
mechanical properties when hardened under the same conditions as
standard equivalents [208].
Luo et al. used corn straw hydrolysis lignin to produce lignin-based
resin. It was mixed with soybean adhesive to obtain a plywood binder.
The resulting binder is characterized by improved water-tightness,
higher thermal stability in hardened state, and a smooth surface with
a lower number of pores and cracks, which prevents moisture penetra­
tion. Adding lignin-based resin also ensures appropriate viscosity of the
binder, which leads to its improved distribution in the plywood hot
pressing process. This causes the formation of stronger bonds with wood,
thus providing the plywood with good wet shear strength (0.65–1.05
MPa) [209].
In another study, Yang et al. obtained phenol–formaldehyde resins in
which phenol was partially (50% wt.) replaced with one of four types of
biorefined technical lignin: corn cob lignin, two different types of poplar
lignin, and wheat straw lignin. The obtained resins containing the
aforementioned technical lignin varieties can be successfully used to
produce plywood characterized by high performance and low formal­
dehyde emissions. The composition of the reactive mixture suggested
based on analysis of the active sites of lignin was of great importance for
the results obtained [210].
Demethylation is a method of lignin modification that enables sig­
nificant improvement in its reactivity by removing methoxy groups and

638
P. Jędrzejczak et al.
Table 4
Overview of corrosion inhibitors based on lignin and its derivatives.
Lignin type Substrate
Ultrafiltrated soda, kraft and organosolv lignin produced Mild steel
from oil palm fronds
Monomers of lignin; p-coumaric acid (CA), ferulic acid Mild steel
(FA) and hydroxybenzaldehyde (HB)
BioPiva™ 190, an industrial grade softwood kraft lignin, Iron-
and pilot-scale hardwood organosolv lignin phosphated
(Fraunhofer Center for Chemical-Biotechnological steel
Processes (CBP), Germany)
REAX® 85 A, REAX® 83 A, REAX® 100 M, REAX® 88 B, Steel bar
REAX® 88 A, five different kraft or sulfite lignins, grade 60
from a paper manufacturing company (MeadWestvaco
Inc., USA)
Kraft and soda lignin extracted from black liquor of oil Mild steel
palm empty fruit bunch
Kraft, soda, and organosolv lignins extracted from oil Mild steel
palm fronds
Organosolv lignin extracted from oil palm fronds and Mild steel
modified by organic scavenger during delignification
Lignin precipitated from alkaline straw pulping black Mild steel
liquor
Organosolv lignin extracted using a mixture of ethanol Carbon steel
and water as a solvent (Dedini SA, Brazil)
Steam-exploded rice straw lignin (Anhui Geyi Carbon steel
Biorefineries Industrial Park Ltd., China)
Lignosulfonates (catalog number 561134 and 561126 Mild steel
from Aldrich)
Lignins extracted by organosolv pulping process of Stainless steel
beech (hardwood) and spruce (softwood) (Fraunhofer
Center for Chemical-Biotechnological Processes
(CBP), Germany)
Lignosulfonate (different Russian pulp and paper plants Carbon steel
in Slotsk, Solikamsk and Arhangelsk)
forming catechol moieties within the macromolecule. Furthermore, the
reaction leads to increased hydroxy group content in lignin [211,212].
Li et al. demethylated sodium lignin under atmospheric pressure using
four types of sulfur-mediated demethylation reagents: sulfur, sodium
hydrosulfide, sodium sulfate(IV), and n-dodecyl mercaptan. In the next
step, the modified lignin was used to obtain fast-hardening demethy­
lated lignin–phenol–formaldehyde (DLPF) resins, where it replaced 30%
wt. of phenol. The resulting resins were then used as plywood binder.
The researchers carefully studied the relationship between the molecu­
lar structure of demethylated lignin and the bond strength of the ob­
tained resin. Based on the results of FT-IR and 13C NMR spectroscopy, it
was concluded that due to demethylation, methoxy groups were effi­
ciently transformed into phenolic hydroxy groups. Increased OH group
content in lignin contributed to improved bond strength and lower
formaldehyde emissions in the resulting plywood, as well as increased
curing time of DLPF resins [211].
International Journal of Biological Macromolecules 187 (2021) 624–650
Conditions Effect of using lignin Reference
0.5 M HCl, 28 ± 2 C ◦
All the cited lignins exhibit better corrosion inhibition [169]
properties and behave as mixed-type inhibitors with
dominant anodic (organosolv lignin) or cathodic
(alkaline lignin) effectiveness.
3.5% NaCl, pH 7, 25 ◦ C The selected monomers are potential steel inhibitors [171]
under nearly neutral conditions and act as mixed-type
inhibitors. Corrosion inhibition efficiencies decrease in
the order CA > FA > HB.
5% NaCl, room temperature Among the tested coatings, the highest corrosion [174]
protection was achieved with the use of kraft lignin,
followed by organosolv lignin. Both types were
previously dissolved in 1-methoxy-2-propanol. It was
found that the kraft lignin-based coating demonstrates
suitable short-term anticorrosive characteristics, but is
unable to provide long-term protection under these
aggressive conditions.
Solutions which simulated A suitable concentration (0.3–0.4 mg/L) of sulfonated [175]
internal conditions of water kraft lignin provides a good barrier layer on the iron
distribution pipelines, pH surface and therefore improves its anti-corrosion
6.7 properties.
3.5% NaCl, pH 6 or 8, 25 ◦ C Both kraft and soda lignin show good corrosion- [176]
inhibiting properties and behave as mixed-type
inhibitors.
0.5 M HCl, 28 ± 2 ◦ C Soda lignin best inhibits mild steel corrosion and exhibits [177]
the highest antioxidant activity among the lignin types.
0.5 M HCl, room Modified organosolv lignin exhibits better corrosion [178]
temperature inhibition properties than unmodified lignin. Moreover,
the modified lignins behave as mixed-type inhibitors with
predominant anodic efficacy.
10% HCl, 25 or 80 ◦ C Lignin–dimethyl diallyl ammonium chloride–acrylamide [179]
terpolymer acts as a good corrosion inhibitor under the
studied conditions. In addition, when the concentration
of lignin terpolymer increases, its ability to inhibit
corrosion also increases.
3.5% NaCl, 25 ◦ C Incorporation of lignin into siloxane-poly(methyl [180]
methacrylate) coatings leads to coatings with low
roughness, increased hydrophobicity, adhesion, hardness
and scratch resistance, and improved corrosion
resistance.
3.5% NaCl, room Lignin nanoparticles act as anticorrosive nanofillers in [181]
temperature epoxy coatings. The epoxy coatings with dispersed lignin
nanoparticles show superior corrosion protection of the
substrate compared to the bare epoxy coatings.
3.5% NaCl, ambient Coatings based on lignosulfonate-doped polyaniline [182]
temperature inhibit the corrosion of coated steel.
Solution simulating body The pure varieties of lignin can form coatings on stainless [183]
fluid or phosphate buffered steel surfaces with excellent adhesion and corrosion
saline, room temperature properties. The coatings exhibit current densities lower
by up to 2 orders of magnitude than bare stainless steel.
Air-saturated brine, room Lignosulfonate electropolymerized on a carbon steel [184]
temperature surface can act as a corrosion-protective coating.
Moreover, as a result of the electropolymerization of
lignosulfonate, a more than threefold decrease in the
corrosion rate was found.
Research by Stücker et al. involved two types of lignin, isolated
through enzymatic hydrolysis and alkaline extraction after water vapour
treatment of non-debarked poplar wood, being used as a copolymer in
the production of phenol–formaldehyde resins (with a phenol substitu­
tion rate of 20% wt.), and in turn, these were used as binders in the
manufacture of particleboards. Despite the fact that resins based on
these lignins exhibit slightly lower reactivity and bond strength
improvement, relative to the reference resin, particleboards bonded
with their use offer good mechanical properties that satisfy the European
requirements for P5 particleboards (particleboards for load-bearing
applications under humid conditions) [213].
Core-shell Fe3O4@lignin nanoparticles can be successfully used to
replace 20% wt. phenol in phenol–formaldehyde resins, in order to
synthesize magnetic PFRs able to absorb electromagnetic waves. The
resulting resins are promising in terms of the development of electro­
magnetic shielded plywood [214].
639
P. Jędrzejczak et al.
A phenol–formaldehyde resin with 50% wt. of phenol replaced by
lignin–phenol–formaldehyde resin (LPFR) was used as a modifier
improving the bond performance of an adhesive synthesized using
soybean flour and polyamidoamine–epichlorohydrin (PAE). Adding
LPFR and PAE improves the adhesive's dry and wet bond strength by
66.3% and 184.2% respectively, as well as increasing the solid content
by 35.5%, which contributes to obtaining an adhesive with viscosity
suitable for industrial applications. The lignin–phenol–formaldehyde
resin primarily reinforces the wet bond strength. The improvement of
this parameter is associated with (i) LPFR and PAE reacting with soy
protein functional groups, resulting in the formation of a cross-linked
structure, and (ii) polycondensation reactions of LPFR molecules,
which further strengthen adhesive cross-linking density, by creating an
interpenetrating structure with cross-linked proteins. In turn, improved
bond strength results from the fact that LPFR easily penetrates the wood
surface, interlocking with it. Increased thermal stability and reduced
crystallinity were found in the case of a hardened adhesive, due to the
use of LPFR and PAE [215].
Hussin et al. used two lignins (kraft and sodium lignin) isolated from
kenaf to partially (10% and 30%) replace phenol in a phe­
nol–formaldehyde resin. Glyoxal was used as a complete formaldehyde
substitute. Two types of adhesive were obtained, namely, kraft lig­
nin–phenol–glyoxal (KLPG) and sodium lignin–phenol–glyoxal (SLPG).
Comparing both lignin types, it was concluded that the sodium variety
exhibited a higher content of phenolic hydroxy groups, higher molecular
weight and higher glass transition temperature, as a result of which the
SLPG resin had a better cross-linked structure. The resin containing 30%
sodium lignin had a higher solid content and viscosity and the shortest
gelation time (53.70%, 3188 mPa⋅s and 46 s respectively). Also, in terms
of mechanical properties, the aforementioned SLPG exhibited the
highest maximum load (7208.57 N), tensile strength (72.08 MPa),
elongation at break (34.40%) and internal bonding (53.83 N/mm2). The
resin with 30% kraft lignin was placed second in terms of these me­
chanical properties [216].
In the synthesis of epoxy resins used as adhesives, the objective is to
replace formaldehyde, an irritant and carcinogenic substrate. This is all
the more important since this substance is released both during
manufacturing and during the use of products containing epoxy resin
[217]. Lignin can be used to produce resins without formaldehyde. Li
et al. used kraft lignin and glycerol diglycidyl ether as a cross-linking
agent in the production of a resin used as an adhesive for wood in
plywood manufacturing. The lignin-based resin exhibited comparable
water tolerance, curing time and bond performance to those of
formaldehyde-based resin. Furthermore, three-layer plywood produced
with the use of the lignin-based resin exhibited maximum shear stress
comparable to that of commercial equivalents [217].
Most epoxy resins globally (above 90%) are produced by conden­
sation of bisphenol A, which is a toxic and environmentally harmful
substance [218,219], with an estrogen-like structure that may disrupt
the functioning of the endocrine system [220]. For this reason, research
has focused on searching for a method to synthesize epoxy resins using
biological compounds. Lignin is suitable for this purpose, owing to its
natural structure rich in aromatic rings [218]. Direct application of
lignin entails challenges associated with its high molecular weight and
heterogeneity. Also, mixing lignin with commercial resins and modi­
fying it with the use of epichlorohydrin is a difficult process. The use of
lignin to produce epoxy resins is also limited by its poor solubility and by
steric hindrance effects caused by functional groups [218]. Zhang et al.
successfully synthesized lignin epoxy resins, using organosolv lignin
unmodified and subjected to various modifications, namely demethy­
lation, phenylation and hydroxymethylation. The obtained resins were
used as polymer grouting materials. Epoxy resin containing up to 16%
wt. non-modified organosolv lignin exhibits thermal stability, as well as
water and chemical resistance. It is characterized by low initial viscosity
(17 mPa⋅s) and good mechanical properties. Compressive and tensile
strength values and bond strength amount to 101.92 MPa, 19.20 MPa
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International Journal of Biological Macromolecules 187 (2021) 624–650
and 3.39 MPa, respectively. The values of these parameters significantly
exceed industry standards. Subjecting lignin to modifications enabled an
increase in the number of functional groups, which led to improved
mechanical and thermal properties. It was concluded that appropriate
modification of lignin can result in the obtaining of polymer grouting
materials suitable for specific applications [218].
One of the latest approaches towards synthesizing lignin epoxy resins
involves lignin depolymerization, aimed at obtaining compounds of
lower molecular weight. Van de Pas and Tor produced epoxy resins
using products obtained through hydrogenolysis of pine wood native
lignin. The lignin-based products reacted with epichlorohydrin to pro­
duce the epoxy prepolymer. The resulting lignin-based epoxy prepol­
ymers were used to partially (from 25% to 75%) replace bisphenol A
diglycidyl ether, which improved the elasticity modulus and flexural
strength by 52% and 38% respectively [221].
In summary, lignin and its derivatives exhibit high potential for
partial or complete replacement of phenol in phenol–formaldehyde
resins in the construction sector. In epoxy resins, lignin enables the
reduction and/or replacement of harmful formaldehyde and bisphenol
A.
3.5. Lignin and its derivatives in asphalt pavement
A number of recent publications show that bioasphalt exhibits
similar properties to petroleum asphalt. Examples of raw materials used
to produce these products, which have successfully replaced crude oil,
include pig manure [222,223], wood chips, sawdust and shavings as a
waste product in lumber mills [224–226], as well as waste edible
vegetable oil [227] and microalgae [228,229]. Lignin is also used in the
pavement industry. Due to the fact that bitumen and lignin have similar
chemical structure, lignin has shown promise as a renewable bitumen
filler and modifier. When the lignin content in a bituminous mass is low,
it serves as a modifier, but when the proportion of lignin exceeds 10%, it
is usually classified as a filler [230]. The concept of using lignin, spe­
cifically kraft lignin, as a filler in asphalt composites was first proposed
by Terrel and Rimsritong in 1979, and resulted from concern over the
price and availability of asphalt [231]. In 1983, a team led by Sund­
strom, driven by similar motivations, conducted a similar study using a
different type of lignin, derived from the steam-exploding process. The
lignin in the asphalt acted as a filler, and constituted up to 50% of the
mix. Increasing lignin content in the sample led to higher viscosity and
lower plasticity. When lignin made up 30% of the asphalt binder, its
properties were similar to those of non-modified asphalt. Furthermore,
that percentage of lignin produced the maximum binder stability [232].
Lignin is part of the lignocellulosic biomass that was used by Ding
et al. to synthesize bio-oil, which was then mixed with petroleum-based
asphalt to produce bioasphalt. The thermal liquefaction method was
applied to synthesize bio-oil from lignocellulose. The next stage of the
study involved preparing bioasphalt by mixing the bio-oil with com­
mercial asphalt. Analysis showed that the resulting material had poorer
thermal stability than a reference petroleum-derived sample. On the
other hand, the viscosity of the bioasphalt gradually decreased with
increasing bio-oil content. As regards the glass transition temperature,
the value of this parameter in the case of the material containing 10% of
the lignocellulose-derived substance was close to that for commercial
asphalt [233].
In turn, Wu et al. used waste lignin from the pulp and paper industry
to partially replace bitumen, where it was used as an alternative filler.
The component ratio in the obtained material (LMA; lignin-modified
asphalt) was 1 part of lignin to 4 parts of petroleum-derived bitumen.
As a result of adding lignin, the bitumen became harder, as was indi­
cated by the results of analysis, including lower permeability and
ductility, as well as higher softening point and dynamic modulus tem­
perature. Lignin modification also led to changed temperature suscep­
tibility. The researchers also studied the anti-aging ability of the
obtained LMA and concluded that it deteriorated in the short term, as
P. Jędrzejczak et al.
compared to its non-modified counterpart. Furthermore, it was found
that this parameter was greatly impacted by the large abundance of
hydroxyl and other chemically active groups exhibited by lignin. In
contrast, in the case of long-term aging, lignin experiences decomposi­
tion, which is favourable for the anti-aging properties of bitumen. The
improvement in this parameter is a result of the presence of carbonyl
groups in LMA. It was also found that lignin was uniformly distributed in
bitumen owing to an appropriate mixing procedure [230]. Batista et al.
also used the pulp and paper industry waste product, namely kraft
lignin, to produce asphalt modified with this compound. An amount of
1%, 4% or 6% wt. lignin was added to the bitumen. This resulted in a
material with higher rutting resistance at high temperatures and higher
thermal cracking toughness at lower temperatures (down to –12 ◦ C)
[234]. The positive results related to the second of the aforementioned
parameters are in contrast with the findings of other research teams,
with the differences possibly arising from the complex lignin structure,
which is impacted by numerous factors. The LMA binder obtained by
Batista's team exhibited higher resistance to photodegradation than its
conventional counterparts. Aging tests suggested that lignin exhibited
antioxidating activity, because it reduces the free radicals formed in
asphalt. The LMA binder containing 6% wt. of lignin exhibited greater
aging resistance [234]. The authors of yet another study used powdered
wood lignin, which acted as a modifier or partial substitute in asphalt,
and amounted to 5% or 10% wt., respectively. A bituminous binder
modified with lignin exhibits higher viscosity and, just like in other
studies, improves rutting resistance at high temperatures. Only slightly
poorer values of the fracture strength were found, whereas the fatigue
strength of the asphalt binder deteriorated as a result of adding lignin.
Ultimately, it was suggested to use lignin as an anti-oxidizing modifier
[235]. Gao et al. studied the impact of four different lignin contents (2%,
4%, 6% and 8%) on the rheological properties of LMA at high temper­
atures and its fatigue performance. They found that adding lignin
resulted in increased viscosity of pure asphalt, and that with its
increasing content, the flow activation energy tended to grow, meaning
that the bituminous mass was more sensitive to temperature changes
and higher flow resistance. Lignin-modified binder is more rigid and
more resistant to deformations at high temperatures. The presence of
lignin in LMA delays oxidizing reactions occurring in the course of
aging, reduces strain from shear forces, and contributes to increased
resistance to permanent strain. Nonetheless, lignin degrades the fatigue
performance of asphalt [236]. Yuanita et al. utilized lignin, taking
advantage of its amorphous nature, as an agent bonding hydrophilic and
polar bitumen with hydrophobic and non-polar polypropylene modifier.
The polymer content was 4% wt., while the content of lignin was 0.1%,
0.3% or 0.5% wt. depending on the sample. The results obtained implied
that adding lignin led to better mixing of bitumen and polypropylene
[237]. Pérez et al. used a liquid waste product with 23.39% wt. lignin,
generated in a fiberboard manufacturing process, to partially replace
bitumen in the asphalt mix. The aforementioned industrial waste was
not subjected to any treatment and was directly mixed with bitumen.
Depending on the sample, the product's lignin content amounted to 0%
(reference sample), 5%, 10%, 20% or 40% wt. relative to the weight of
bitumen. It was shown that a mix with 20% wt. of the waste product
(20% LMA) offered better resistance to moisture and required lower
bitumen content to achieve adequate waterproofness, compared to the
reference mix. The thermal susceptibility of the sample with that per­
centage content of filler also decreased; therefore, the fatigue strength at
low temperatures and resistance to permanent strains at high tempera­
tures improved. After six months, the differences in these properties
between the 20% and 0% samples became less clear. Based on the results
obtained, the authors concluded that the 20% LMA mix offered the best
properties for roads with average and low traffic volume [238]. Yet
another study estimated the impact of 10% wt. kraft lignin on the
chemical and rheological properties of post-aging bitumen. It was
concluded that the microstructures of bitumen with kraft lignin and
bitumen without the addition of that compound were very similar.
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International Journal of Biological Macromolecules 187 (2021) 624–650
Adding lignin both prior to and after aging has little effect on the
viscoelastic properties of bitumen, and the physical interactions be­
tween these compounds were significant. Nonetheless, adding lignin
resulted in a slight reduction in fatigue strength. It was found that the
beneficial effect of lignin on the relaxation properties was limited, while
the aging of that compound and the time of its addition highly impacted
this feature. Moreover, adding lignin contributed to improved cracking
toughness. It was also observed that lignin exhibited antioxidizing ac­
tion in bitumen [239]. The authors of another paper added three lignin
variants – (i) commercially available kraft lignin, (ii) lignin precipitated
from black liquor in the laboratory, and (iii) lignin isolated from rice
husks using a deep eutectic solvent – to an asphalt binder, where they
partially (2%, 4% or 6%) replaced bitumen. It was found that all of these
lignin types improved asphalt performance at high temperatures. Add­
ing the second and the last of the lignin variants mentioned above
positively affected the long-term aging index. This study showed that an
asphalt mix obtained by adding to the binder an amount of 6% lignin
precipitated from black liquor in the laboratory satisfied the re­
quirements on moisture resistance, improved rutting resistance and
cracking toughness, and enabled the most favourable elasticity index to
be obtained [240]. In another study, McCready and Williams used four
different by-products of ethanol production. Three of them contained
10–15% lignin after processing, while the last did not contain lignin and
constituted a control sample. The products were mixed with a binder at a
weight ratio of 3%, 6% or 9%. The addition of lignin-containing mix­
tures to the asphalt binder resulted in increased rigidity. Modification
also improved asphalt performance at high temperatures, although low-
temperature performance deteriorated slightly. It was concluded that
the by-product containing lignin widened the temperature range of the
obtained bitumen [241].
In a further publication, Pan described research conducted by his
team aimed at studying molecular oxidation and antioxidation mecha­
nisms in the presence of various antioxidants. The motivation behind
this study was to explain the chemical fundamentals of the oxidization of
the composite material and to identify efficient antioxidants for use in
asphalt. Lignin rich in coniferyl alcohol groups was chosen as such a
substance, owing to the large number of phenolic structures, providing it
with significant antioxidizing ability. Ultimately, it was concluded that
this lignin variant could be used as an antioxidant in petroleum asphalt.
Nonetheless, non-oxidizing conditions for lignin (temperature below
130 ◦ C and pressure lower than 1 atm) should be maintained in order to
achieve maximum efficiency in scavenging free radicals [242].
Attempts have also been made to add fractionated or modified lignin
to asphalt. For example, Yuliestyan et al. subjected kraft lignin to the
Mannich reaction using an intermediate product formed by reacting
formaldehyde and TEPA (see Fig. 9), in order to improve its solubility in
an acidic environment. Using modified lignin as a cationic emulsifier
enabled the efficient production of bitumen emulsions with a bitumen
content of up to 70%. At the final stage, the obtained dispersion systems
were used to produce HWMA (hot warm mixed asphalt) samples, also
containing fresh aggregate or constituting 100% reclaimed asphalt
pavement (RAP). The application of the second of the aforementioned
materials positively impacted mechanical strength [243]. This study was
continued in a subsequent paper by Yuliestyan et al. Modified kraft
lignin (MKL) was used as a stabilizer of a bitumen emulsion that was
used to produce asphalt at a reduced temperature (80–130 ◦ C) and being
100% RAP. Based on measurement of surface activity, it was concluded
that the effect of MKL in the emulsion may improve the wettability of the
bitumen-coated aggregate [244]. In turn, Wang et al. used amine lignin,
synthesized via the Mannich reaction. Amine lignin was used as a
cationic emulsifier to produce emulsified asphalt [245,246]. Next, used
cooking oil, which is used to improve the condition of asphalt pave­
ments, was added to the emulsion [245]. A very advanced research
project using modified lignin was conducted by Xie et al., where kraft
lignin was fractionated and modified, to enable its use as a modifier
improving the efficiency of an asphalt binder. Furthermore, the
P. Jędrzejczak et al. International Journal of Biological Macromolecules 187 (2021) 624–650

Fig. 9. Predicted molecular structure of compounds during a Mannich reaction leading to modified kraft lignin. TEPA (tetraethylenepentamine), where R1 =
C2nH1+5nNn, R2 = C2(4-n)H1+5(4-2)N4-n for 0 ≤ n ≤ 2 with three secondary and two primary amines, and R = the remainder of the lignin molecule, reproduced with
permission [243].
Copyright 2017, Elsevier.

researchers suggest biological and chemical processes for dividing lignin
into fractions differing in molecular weight and chemical properties. The
driving force behind the study was the fact that individual lignin por­
tions can be used as modifiers significantly improving asphalt perfor­
mance at low and high temperatures. Non-modified kraft lignin, which
was added to the binder in varying amounts (5–20%), improved the
high-temperature performance (rutting resistance) of the asphalt binder.
Unfortunately, adding more than 5% kraft lignin significantly impaired
the resistance of this material to low-temperature cracking. Therefore, it
was concluded that raw kraft lignin is not suitable for use as a modifier
in bituminous binders. To improve the efficacy of lignin in this appli­
cation, it was subjected to a biological or chemical process. The first
method used laccase-1-hydroxybenzotriazole (HBT) to separate a
portion with a similar molecular mass and functional groups from the
kraft portion. The operation enables fractionation and dissolution of
more than 35% of kraft lignin. The chemical process involves formic
acid and Fenton's reagent (iron ions and H2O2) for kraft lignin frac­
tionation. This leads to lignins that are soluble or insoluble in water.

Fig. 10. The impact of pristine kraft lignin and the obtained fractions on the features of asphalt binder, HBT – 1-hydroxybenzotriazole, based on [247].

642
P. Jędrzejczak et al.
Fractions from both processes were tested for use as an asphalt binder
modifier. The results for aging resistance and high- and low-temperature
performance are shown in Fig. 10. Furthermore, it was concluded that
binder rigidity increases with increasing lignin content. The results
indicate that the greatest potential for application as an asphalt binder
modifier is demonstrated by the soluble lignin fraction obtained in the
biological process and by the chemically derived insoluble fraction. The
paper also suggests a mechanism describing how the molecular weight
of lignin and functional groups can impact asphalt binder performance
[247].
Yet another approach is presented in a paper by Xin et al., who used
lignin obtained by enzymatic hydrolysis to produce epoxy resin, which
was then used as an asphalt binder modifier, combined with bisphenol A
epoxy resin. A bio-anhydride synthesized from a maleic anhydride and
eleostearic acid methyl ester was used as the hardening agent. To in­
crease the lignin's solubility in organic solvent and make hydroxyl
groups better accessible for modification, the lignin was subjected to
partial depolymerization. The method of synthesis of lignin-based epoxy
resin and modified asphalt is shown in Fig. 11a. Epoxy resin containing
lignin exhibits similar asphalt modification capacity as its commercial
counterpart, bisphenol A. Modifying asphalt with the lignin-based epoxy
resin significantly improved its viscoelastic properties, which is partic­
ularly evident at elevated temperatures [248].
Kowalski et al. added green components, such as reclaimed asphalt
pavement (RAP), lignin, construction and demolition waste (C&DW),
and bio-binder obtained from vegetable oils, to an asphalt mix in order
to obtain an eco-innovative material. Lignin was used to partially
replace styrene–butadiene–styrene (SBS) copolymers. The results
Fig. 11. The route of synthesis of partially depolymerized lignin-epoxy and epoxy asphalt (a), HAc – acetic acid, reproduced with permission [248]. Copyright 2016,
American Chemical Society. Graphical representation of the concept of eco-innovative asphalt pavement structure, HMA – hot mix asphalt, RAP – reclaimed asphalt
pavement, C&D waste – construction and demolition waste (b), reproduced with permission [249].
Copyright 2016, Elsevier.
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International Journal of Biological Macromolecules 187 (2021) 624–650
obtained in the case of optimal lignin-modified asphalt samples satisfy
the stability requirements for the storage period. Furthermore, the
values of all parameters – penetration at 25 ◦ C, softening point, elastic
recovery, and storage stability – are in accordance with PG-3 (Spanish
Specifications for Road and Bridge Construction). This publication also
reviews a concept for an environmentally safe asphalt pavement, which
is summarized in the following points [249]:
• The surface course is supplemented with a “green” bitumen modifier,
which is a waste product of bioethanol production with high lignin
content (approx. 52–54%) – an alternative to traditional additives.
• The application of a bio-fluxing agent in the binder course and the
asphalt base course allows the introduction of more recovered
asphalt pavement.
• The lower courses (sub-base and sub-grade) are composed primarily
of a construction and demolition waste material.
A concept for such an eco-asphalt is shown in Fig. 11b.
Lignin's high potential for use in asphalt is proven by the achieve­
ments of the Bioasphalt Zeeland project, which successfully developed a
process for synthesizing lignin with the same properties as bitumen.
Bioasphalt based on such lignin can be used at a temperature 30 ◦ C lower
than the conventional material. The use of lignin enabled not only the
replacement of fossil fuels, but also the reduction of CO2 emissions. The
fact that in 2015 a 70-meter section of bioasphalt was built under the
project (at Sas van Gent in the Dutch province of Zeeland), and that it
became a part of a heavy traffic road, proves how advanced this project
is [250]. On the other hand, the first bicycle lane made of the developed
P. Jędrzejczak et al.
material was built at the Wageningen University and Research Campus
in 2017 [251], and since 26 November 2020, the Dutch city of Vlissin­
gen has had a pavement section made entirely of bioasphalt with kraft
lignin in all of its layers, with some of them even containing recycled
asphalt [252].
The construction industry, in particular roads and pavements, faces a
major challenge associated with the depletion of crude oil along with
technological progress in the field of refining and processing, resulting
in the production of fewer fractions suitable for this sector. As a result,
the price of bitumen is on an upward trend. Lignin, which similarly to a
certain bitumen fraction consists of aromatic rings combined with
aliphatic chains, as discussed above, is a substance that can partially
replace bitumen in asphalt production. It is certain that lignin will gain
in importance as a bitumen replacement in the near future, and much of
this will hinge on the selection of the correct lignin type, source and
extraction method to match the lignin structure to the required prop­
erties of the bitumen substitute.
4. Life cycle assessment in the construction industry
The construction industry is responsible for the consumption of
30–40% of global energy and for 40–50% of greenhouse gas emissions
[253,254]. Life Cycle Assessment (LCA) is used to assess and evaluate
the environmental impact of a product throughout its life cycle from
cradle to grave. In the case of building structures, LCA includes the
extraction of raw materials, production of materials, construction and
operation of structures, and their utilization [253,255,256]. LCA con­
sists of four main steps, namely: (1) defining the purpose and scope of
the analysis; (2) creating a life cycle inventory; (3) impact assessment;
and (4) interpretation and analysis of the results [253,254,257].
The life cycle assessment framework for the construction industry is
presented in Fig. 12. Two approaches to life cycle assessment are
distinguished. The first is the problem-oriented mid-points approach,
which translates environmental impacts into real phenomena, such as
global warming, acidification, ozone depletion, eutrophication and
human toxicity. In contrast, the damage-oriented end-points approach
translates into damage modeling the impact of the mid-point on people,
the environment, climate change and resources [254].
One of the first works devoted to the application of life cycle
assessment in construction is a 1982 study by Bekker [258]. Neverthe­
less, it was not until the 21st century that the use of LCA for assessing the
degree of sustainability of buildings rapidly increased [256]. General
procedures for conducting life cycle assessment have been standardized
in ISO 14040 [259] and 14,044 [260]. However, there have been con­
cerns that the LCA methodology described in the above-mentioned
standards may not be suitable for complex projects such as buildings
Fig. 12. Framework for the building industry, reproduced with permission [253].
Copyright 2015, Elsevier.
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International Journal of Biological Macromolecules 187 (2021) 624–650
[261]. The attributes of construction and building projects which in­
crease the complexity of the individual stages of LCA include [256]:
(1) The fact that many different materials are used to manufacture
buildings, which are built in different countries, and that the very
creation of these structures involves many processes. For this
reason, a significant amount of data is required to be collected.
(2) The uniqueness of buildings in terms of time, place and function
makes the improvement of the LCA process difficult and the
benchmarking problematic.
(3) Buildings have a long and unknown service life, which makes it
difficult to predict some variables and parameters.
(4) The functions of buildings and the way they are used may change
over the years, but even if they were constant over time, they
would still have a significant impact.
(5) Moreover, there is a complex relationship between the indoor
environment and the outdoor environment.
For this reason, the European Committee for Standardization is
developing a package of standards for use in the construction industry
(CEN/TC 350 Sustainability on construction works), which cover topics
such as environmental, economic and social LCA, LCA calculation
methods and others [256].
In recent years, many works regarding the implementation of life
cycle assessment in construction have been published. For example,
Rashid and Yusoff found that the greatest amount of energy is consumed
during the use phase. It was also noted that in cold regions, space
heating consumes the most energy, while in tropical regions with higher
temperatures, heating does not play such an important role. Although
concrete in itself has a low initial embodied energy, it makes the overall
highest contribution to initial embodied energy due to the large quan­
tities used in construction [253].
In contrast, the work of Schiavoni et al. used the available LCA data
to compare the environmental performance of different insulation ma­
terials. Natural pumice, cellulose fluff, kenaf and glass wool were
identified as the best insulators for the cradle-to-gate approach, which
ignores the effects of transportation, use and disposal. On the other
hand, in the cradle-to-grave approach, which includes the stages of
transport and utilization, the lowest embodied energy values were found
for sheep wool and recycled fabrics. In this approach, hemp and stone
wool are the best insulating materials in terms of the potential to create a
greenhouse effect [255].
The team of Hossain was the first to use life cycle assessment tech­
niques to estimate the environmental impact of producing aggregate
made of glass waste. Moreover, two other types of aggregate were
subjected to LCA analysis in that study: freshly extracted in a quarry, and
P. Jędrzejczak et al.
obtained from construction and demolition (C&D) wastes. The materials
were assessed in terms of their potential use in road construction as a
sub-base material and in lower-quality concrete products, such as con­
crete cubes. Based on the LCA results, it was found that the generation of
aggregates by recycling C&D waste instead of using quarry aggregate
enables a reduction in the net environmental impact by approximately
49–51%. On the other hand, the use of waste glass to produce 1 ton of
aggregate reduces energy consumption by 185 MJ and greenhouse gas
equivalent by 14 kg CO2, compared to river sand [254].
As regards LCA assessment relating to the sustainability of the use of
lignin in construction, the number of publications on this topic is very
limited, and the existing ones concern insulation materials. In work by
Zhang et al., a polyisocyanate based on 4,4′ -diphenylmethyl diisocya­
nate (pMDI) was used to produce surface-functionalized kraft lignin
(SFL), which was then used to partially replace (0–40%) crude oil-based
polyols in the synthesis of rigid polyurethane foams (RPUFs). The LCA
assessment shows that the use of such modified lignin is preferable to the
traditional methods of polyurethane production in terms of both envi­
ronmental protection and human health, especially as regards acidifi­
cation, eutrophication, global warming, photochemical oxidation,
carcinogens, and effects on the respiratory system. In addition, it was
found that the functionalization of the lignin surface has a lower impact
on the environment and human health, relating to ecotoxicity and
carcinogen production respectively, compared with two competing
methods of lignin modification: liquefaction and oxypropylation pro­
cesses. RPUFs based on SFL show a lower impact on the production of
non-carcinogenic substances than foams composed of oxypropylated
lignin [150].
The team of Shanmugan focused on sandwich panels used for insu­
lation purposes, consisting of a polyurethane foam core sandwiched
between two epoxy composite skins made of glass fibers (GF) and
silanized fly ash (SFA) in epoxy resin. Kraft lignin and organosolv were
used to produce epoxy resin constituting the polymer matrix in the skins.
Based on the LCA assessment, it was found that the production of panels
in which coatings are based on epoxy resins synthesized using the
analyzed varieties of lignin reduces the global warming potential by
57% compared to panels with petroleum-based epoxy skins. Neverthe­
less, lignin-containing panels show greater potential impact on land use
than the reference steel-skinned panels. When the petroleum epoxy resin
is replaced with products containing lignin, the influence of parameters
such as the freshwater eutrophication potential and freshwater ecotox­
icity doubles. Panels with kraft-based epoxy resin skins have a greater
environmental impact than their organosolv counterparts in the
following categories: global warming potential, particulate matter for­
mation potential, photochemical ozone formation potential, and acidi­
fication potential. Summarizing the results of the LCA assessment,
organosolv lignin epoxy resin is more environmentally friendly than the
epoxy resins based on petroleum and steel which are used to make skins
in sandwich panels [262].
Manzardo et al. focused on the lack of uniform studies involving new
polyurethane materials, the synthesis of which is based on the use of
renewable materials, including lignin, in terms of their environmental
impact. The objective of their work was to determine which parameters
should be taken into account when designing new, bio-based rigid
polyurethane foams for use as insulating construction materials, so that
the obtained products exhibit better environmental parameters relative
to their petrochemical equivalents. A framework standardizing life cycle
assessment methodology and laboratory testing was developed for this
purpose. The compared factors were: emission of greenhouse gases
(GHG), ozone-depleting gases (ODG), acidifying gases (AG), eutrophi­
cation potential in phosphate equivalents (EPPE) or nitrate equivalents
(EPNE), ozone creating potential (OCP), and the abiotic depletion po­
tential (ADP) of fossil fuels (ADPFF). To study the environmental
impact, three formulas were prepared. These contained different
amounts of lignin (16%, 19% and 20%), with the second polyhydric
alcohol being polyols obtained from azelaic acid (contents of 69%, 78%
645
International Journal of Biological Macromolecules 187 (2021) 624–650
and 78% respectively) [263].
The life cycle assessment found that rigid polyurethane foams pro­
duced with mixtures containing 20% lignin exhibited an improvement
in terms of almost all of the analyzed factors, compared to their fossil
equivalents. The changes in individual parameters are presented in
Fig. 13. Here, sensitivity analysis indicated that foam density and con­
ductivity were key parameters that impacted all environmental factors
[263].
The application of life cycle assessment is important in terms of
estimating the environmental impact of various solutions and materials.
Despite the high complexity of LCA when applied to construction, the
significance and utilization of this technique in this sector, especially in
terms of new approaches and materials, can be expected to grow in the
coming years. It will certainly be important to create and develop
appropriate databases and tools, as well as to increase their availability.
5. Summary and prospects for further research
Growing environmental awareness is leading to increasing numbers
of scientific reports relating to lignin. According to the SCOPUS data­
base, over 13,000 papers with the phrase “lignin used for construction
application” had appeared before June 29, 2021. The increase in the
number of citations with the aforementioned term over recent years has
been very rapid, as demonstrated in Fig. 14. In the case of cement
composites, it is crucial to look for new additives and admixtures that
will improve the properties of the end product and make it more sus­
tainable, since the substances currently used are usually synthesized
from crude oil. Research on modified lignin, in combination with other
compounds in hybrid systems, as admixtures for cement composites can
be expected to develop in the coming years, as it is an interesting and
future-proof approach that enables the creation of durable cement
composites.
Lignin is likely to start replacing conventional, usually petroleum-
derived, materials in the manufacture of rigid polyurethane foams in
the near future. This change arises from the increasing concern for the
natural environment, as well as economic issues associated with the
depletion of crude oil and the growing price of that resource and ma­
terials derived from it. Current research shows that RPUFs containing
lignin exhibit similar properties to commercial petroleum products.
Lignin also enables the production of more environmentally friendly
corrosion inhibitors and protective coatings. The manufacture of these
materials should be increasingly based on using renewable raw
Fig. 13. Radar chart comparison of the environmental impact of rigid poly­
urethane foams (RPUFs) produced from fossil fuels and those containing lignin,
GHG – emission of greenhouse gases, ODG – emission of ozone-depleting gases,
AG – emission of acidifying gases, EPPE – eutrophication potential in phosphate
equivalents, EPNE – eutrophication potential in nitrate equivalents, OCP –
ozone creating potential, ADP – abiotic depletion potential of elements, and
ADPFF – abiotic depletion potential of fossil fuels, reproduced with permission
[263].
Copyright 2019, American Chemical Society.
P. Jędrzejczak et al.
Fig. 14. Search results for ‘lignin used for construction application’ in the
SCOPUS database from 2010 to 2021 [264].
materials, including lignin and its derivatives, which will allow an in­
crease in the sustainability of their development.
It is likely that in the coming years there will be further intensifi­
cation of research on the use of lignin for producing sustainable phenol-
formaldehyde and epoxy resin equivalents for construction applications,
in order to address both the environmental and human health issues
associated with these materials.
Cost and environmental concerns are also drivers of the use of lignin
and its derivatives as a drop-in replacement for bitumen in asphalt.
Increasing the use of lignin in construction has a double benefit: first, it
will increase the level of sustainability in construction, and second, it
will contribute to finding new applications with high added value for
lignin. Moreover, lignin makes it possible not only to obtain “greener”
materials, but also to improve some parameters relevant to the appli­
cation of the materials discussed in this review.
Acknowledgements
This work has been conducted within a project financed from the
funds of the National Science Centre, Poland No. 2019/35/B/ST8/
02535. MNC would like to acknowledge support by Irish Government
funding, DAFM grant, 2019PROG704.
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