Current Opinion in Colloid & Interface Science 19 (2014) 409–416

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Current Opinion in Colloid & Interface Science

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

Lignin: Recent advances and emerging applications

Magnus Norgren ⁎, Håkan Edlund ⁎
Fibre Science and Communication Network (FSCN), Mid Sweden University, SE-851 70 Sundsvall, Sweden

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

Article history: In this paper, we focus on the recent advances on the physical chemistry of lignin. Emerging trends of incorporating
Received 12 May 2014 lignin in promising future applications such as controlled release, saccharification of lignocelluloses, bioplastics,
Received in revised form 20 August 2014 composites, nanoparticles, adsorbents and dispersants, in electro-chemical applications and carbon fibers, are
Accepted 24 August 2014
also reviewed. We briefly describe the complexity of the lignin structure that influences the solution behavior,
Available online 4 September 2014
both as a macromolecule and a colloid, as well as the potential of being a renewable precursor in the development
Keywords:
of high-value applications. Special attention is paid on summarizing the present knowledge on lignin colloidal
Lignin stability and surface chemistry.
Self-aggregation © 2014 Elsevier Ltd. All rights reserved.
Colloidal stability
Lignin surface chemistry
Carbon fibers

1. Introduction 2. Lignin molecule architecture

Lignin is the second most abundant natural polymer after cellulose,
and it is mainly found in the cell wall of woody tree species. The main
source of lignin readily available for use on a larger scale comes from
spent pulping liquors and chemical liberation of wood fibers from the
pulp and paper industries, and the global production of lignin-based
materials and chemicals exceeds 50 million t per annum. Lignin has
not yet been converted into high-value products on a large-scale and
today lignin is mainly used for energy recovery at the pulp mills.
However, as the price of oil increases, the demand for sustainable and
renewable resources consequently increases. A huge opportunity for
securing vast quantities of this raw material at economically viable
rates is from the pulp and paper industry. This could be seen in light
of the ongoing discussion about the development of biorefineries and
the integration of biomass conversion processes to produce power,
heat, biofuels, materials and value-added chemicals from biomass [1–3•].
The ambition in the present paper has been to focus on and summa-
rize the recent advances in surface and colloid chemistry of lignin, as
well as the emerging trends of incorporating lignin in new applications.
In Section 2, we present the lignin macromolecule as a biomaterial re-
source and the possibilities and constraints in colloidal chemistry.
Section 3 is describing the self-association of lignin in solution into
aggregates and particles, as well as the solid lignin surface chemistry.
In Section 4, some ongoing development of lignin into applications of
higher values is discussed. The paper is concluded in Section 5.
⁎ Corresponding authors.
E-mail addresses: magnus.norgren@miun.se (M. Norgren), hakan.edlund@miun.se
(H. Edlund).
Lignin is a highly branched and amorphous biomacromolecule with
variable composition dependent on the plant source [4,5]. Lignin is
unique as a plant cell wall biopolymer due to its heterogeneity, lack of
defined primary structure and aromatic functionality. However, lignin
can be rationalized as the polymerized product of the three basic
phenylpropane monomers as repeating units known collectively as
“monolignols”: p-coumaryl alcohol, coniferyl alcohol and sinapyl
alcohol.
These three monolignols account for the majority of the repeating
units making up the lignin polymer molecules; however, other lignols
may be present in smaller quantities. The proportion of different
monomers in lignin varies considerably depending upon the type of
plant material and there are many possible inter-connecting patterns
between individual units giving an additional complexity to the final
molecule. A representation of molecular fragment kraft lignin, the
most common technical lignin, illustrating different important linkages
is shown in Fig. 1.
It must be noticed that naturally occurring lignin in its unaltered
form is still beyond the realms of possibility to directly study. The
isolation of lignin from native sources results in chemical modification
of the three-dimensional network through the cleavage of bonds
between different lignin monomers, or the covalent attachments to
polysaccharides, creating differently sized lignin fragments. However,
numerous analyses of different isolated lignin samples over the past
decades have led to extensive knowledge of the prevalence of different
covalent linkages.
As mentioned earlier, the main source of lignin readily available for
use on a larger scale comes from spent pulping liquors after chemical
liberation of wood fibers. By far, the most important pulping methods

http://dx.doi.org/10.1016/j.cocis.2014.08.004
1359-0294/© 2014 Elsevier Ltd. All rights reserved.
410 M. Norgren, H. Edlund / Current Opinion in Colloid & Interface Science 19 (2014) 409–416

M
MeO O
OH 3.1. Self-association of lignin into aggregates and particles
CH
C 2
For polyelectrolytes carrying weekly acidic groups, the dissociation
OM
Me
HC O
OMe and, thus, the solubility is governed by an increase of the hydroxide
H2C
HOH
O C C CH2 ion concentration. This is also the case for, e.g., kraft lignins. The polydis-
H
CH H H
O
OH persity of kraft lignins will, of course, also introduce differences in the
O OH
H
OMe solubility and colloidal stability characteristics within the macromolec-
eO
Me O ular distribution of the fragments. Numerous studies dealing with the
OH
C=O
C
colloidal behavior of kraft lignin derivatives have earlier been presented
CH2OH HC in the literature [5–19]. Some earlier studies highlighted the physico-
CH
H2 O
OMe
OOC
HO C OH CH
C chemical characterization of fractionated kraft lignin [20] and the fact
O
OH
M
MeO HC O that kraft lignin after depolymerization is solubilized mainly through
CH
OH O
OH dissociation of phenolic groups [21•]. For decades it has been known
OH
M
MeO that in the presence of high concentrations of monovalent metal ion
O
OH
salts at pH neutral conditions, kraft lignin starts to coagulate and finally
C OH
CHO
HO C
CH precipitate [5]. Moreover, by elevating the temperature in alkaline kraft
HC CH C 2O
CH OH lignin solutions the dissociation of phenolic groups decreases, some-
O
OMe
e times to levels below the threshold of solvency [21•]. From the work
S CH COOH
H
of Lindström it was shown that colloidal kraft lignin, in conformity
CH2OH
O
with other colloids, exhibits a strongly marked critical coagulation con-
centration of added electrolytes (CCC) [9]. More recently, Norgren et al.
Fig. 1. A structural model of a technical lignin fragment (kraft lignin) showing examples of
showed that the experimentally observed phase behavior of colloidal
important intra-molecular linkages [6].
kraft lignin can be described reasonably well by a theoretical approach
derived from the DLVO-theory [13•]. Moreover, the colloidal stability
are kraft and sulfite cooking. The content of the most important
of lignin is also strongly affected by specific ions (Hofmeister effects)
functional groups present in the lignin materials, such as the phenolic
[15•], and these effects are especially pronounced for anions, e.g. sulfate
hydroxyl, carboxyl and sulfonate groups varies with the pulping process
[16].
applied. Kraft lignin is usually isolated by precipitation that remains
During self-aggregation of colloidal particles into larger clusters
after cooking through acidification and protonation of phenolic groups.
due to Brownian motion, two well-defined limiting regimes of kinet-
Depending on the pH value to which the spent liquor (black liquor) is
ics have been identified: the rapid diffusion-limited cluster(colloid)–
acidified, a different composition and yield of the lignin is obtained. A
cluster(colloid) aggregation (DLCA) forming loosely jointed and
hydrosoluble form of lignin that contains a large number of charged
highly disordered structures and the reaction limited aggregation,
groups, the lignosulfonates, is prepared from the by-products of the sul-
RLCA, forming somewhat denser aggregates. It has further been
fite pulping process where the lignins are sulphonated, degraded and
shown that the described processes are universal in the sense that
solubilized. The organosolv process is a pulping process using aqueous
they are independent of the detailed nature of the colloid, if the essential
organic solvents with the lignocellulosic biomass separating the lignin
physical interactions are the same [22]. The two mentioned classes of ag-
fragment via solubilization. The homogeneity of the organosolv
gregation processes and their crossover behaviors are suggested to be
processed lignin is higher than that of kraft lignins and lignosulfonates.
sufficient to describe the complete range of kinetic aggregation [22–
The weight-averaged molecular weight of the lignosulfonate poly-
24]. The DLVO-theory has been a great source of understanding to
mers is typically in the range of 5–400 kDa compared to 1–5 kDa for
RLCA. Additional stabilizing effects such as steric stabilization, might,
the kraft lignin and 0.5–3 kDa for the organosolv lignin. The polydisper-
however, also be contributing [25].
sity for lignosulfonate and kraft lignin is high compared to the
By monitoring the kinetics of kraft lignin aggregation using quasi-
organosolv lignin. The watersoluble lignosulfonates are today, by far
elastic light scattering (QELS) and through the analysis of the mass
the most used types of technical lignin polymer and they are utilized
fractal dimensions of formed aggregates, Norgren et al. showed
in many low-value applications.
that also lignin aggregation follows RLCA and DLCA [14••]. Images
Still today, the available technical lignins are always by-products,
of kraft lignin fractal clusters were also obtained by the Cryogenic
and the properties of the lignin produced are, thus, substantially
Transmission Electron Microscopy (CryoTEM). The resemblance be-
dependent on the core process that is mainly dedicated to pulp and
tween the TEM picture of a DLCA fractal gold colloid cluster with
paper production. A change is foreseen in the future that an increased
fractal dimension df = 1.75 ± 0.05 from Weitz el al. [26] in Fig. 2a,
and quality improved feedstock of raw material as lignin for biorefinery
and the obtained DLCA lignin aggregate in Fig. 2b, df ≈ 1.9, deter-
applications comes from different biorefinery processes.
mined from quasi-elastic light scattering is striking [11].
Due to the chemical and physical heterogeneity of kraft lignin, self-
3. Surface and colloid chemistry of lignin aggregation in kraft lignin systems is complex. The presence of larger
macromolecules is proposed to determine the onset [27]. Depending
One fundamental principle about polymers, in general, is that they on the kraft lignin sample composition, nuclei either may be present
dissolve spontaneously in a solvent if the free energy of mixing from the beginning or may be formed due to changes in the solution
(ΔGmix) is negative. The phase transition is mainly due to the increased conditions. Norgren et al. have proposed different modes of kraft lignin
configurational entropy of the polymer chain or, for charged polymers, aggregation starting from macromolecular kraft lignin and finally
an increase in counterion entropy due to dissociation. The dissociation reaching fractal kraft lignin clusters [14••]. It has also been shown that
of weakly acidic functional groups on colloid surfaces is also a it is possible to stabilize kraft lignin and re-dissolve lignin aggregates
prerequisite for sufficient electrostatic double biorefinery layer repul- if proper additives are introduced to the lignin solution [17•]. Introduc-
sion, maintaining stability and reducing self-aggregation in colloidal ing bile acid salts to aqueous kraft lignin solutions, new possibilities in
systems. Knowledge of the surface chemistry of the material is, controlling the colloidal stability at solution conditions that are other-
therefore, highly important. In this section, the abovementioned aspects wise detrimental for keeping kraft lignin soluble or dispersed, are
related to lignin are reviewed and discussed based on the recent achieved. The interaction between lignin and bile salts is discussed
advances in lignin physical chemistry. due to association at hydrophobic sites in the lignin structure, which
 M. Norgren, H. Edlund / Current Opinion in Colloid & Interface Science 19 (2014) 409–416
Fig. 2. (a) TEM micrograph of a fractal gold colloid cluster [26]. Reprinted with permission from Weitz, DA, Huang, JS, Lin, MY, Sung, J. Limits of the Fractal Dimension for Irreversible Kinetic
Aggregation of Gold Colloids. Physical Rev Lett 1985; 54:1416-19. Copyright 2014 by the American Physical Society. (b) Cryo-TEM image of a fractal cluster of kraft lignin (unpublished).
then increases the hydrophilicity of the associate formed. The efficiency
of bile salts in stabilizing and re-dissolving kraft lignin mostly seems to
be determined by the hydrophilic — lipophilic balance in the different
bile salts, e.g., the number of hydroxyl groups in the skeleton which is
optimally, two. However, geometrical parameters, such as the length
of the polar chain, favoring bile salts with a relatively long, flexible
chain including a conjugated amino acid, are also found to be important.
Even if kraft lignin represents, by far, the greatest amount of techni-
cal lignins produced, the lignosulfonates are the most exploited and
commercialized source of lignin today, mainly due to their solubility
in water at a wider pH range, and the generally higher molecular
weights. The lignosulfonates are prepared from the byproducts of the
sulfite pulping process, which involves the use of solutions containing
sulfur dioxide and hydrogen sulfite ions at elevated temperatures. The
lignin becomes sulfonated and, as such, is soluble in water and under
a range of aqueous solution conditions. In a recent work, Myrvold dis-
cusses the solubility of lignosulfonates as being dependent on whether
other ions are present. Furthermore, Myrvold discusses that the differ-
ences in the solubility influence the measurements of the physical and
chemical properties of the lignosulfonate molecules [28]. Yang et al.
focused on the physicochemical properties on fractionated calcium lig-
nosulfonates [29] and Yan et al. studied the behavior of lignosulfonate
fragments aggregated to macromolecules in an aqueous solution con-
cluding that increasing pH leads to the expansion of the aggregates
cores due to the ionization of weak dissociating acidic groups [30].
Lignosulfonates are primarily used as oil well drilling additives, con-
crete additives, dyestuff dispersants, agricultural chemicals, animal feed
and other industrial binders [4]. The fraction of sulfonation is increased
with decreasing molecular weight [31]; in other words, the solution be-
havior is linked primary to the molecular weight. In some recent papers
about coal water slurries, the importance of molecular weight for the
dispersing efficiency is discussed [32•–34]. Molecular weight-
fractionated samples were investigated, and the adsorption behavior
of the dispersants in the coal–water interface was demonstrated as
the key factor affecting the dispersing effect. Ouyang et al. showed
that sulfonated alkali lignin used as dispersants for cement, contributes
to higher adsorption onto cement particles and hence better dispersion
effects on the cement matrix than the unsulfonated alkali lignin [35].
Matsushita and Yasuda prepared lignosulfonates from acid hydrolysis
lignin, resulting in better dispersibility for gypsum paste, especially at
higher molecular weights and sulfur content [36]. In a recent paper by
Qiu et al., the aggregation behavior of lignosulfonates is thoroughly
discussed [37].
A first step toward an organosolv process was patented by Kleinert
and Tayenthal, who proposed ethanol as a delignifying solvent [38].
Comprehensive descriptions of the organosolv pulping and recovery
411
process are given in a 1971 patent by Kleinert [39] and later in the
paper about organosolvent pulping [40]. An early review of the
organosolv pulping development was presented by Aziz and Sarkanen
[41], who concluded that the re-evaluation of alkali–alcohol systems
was necessary due to the recent developments. The properties of
organosolv lignin are different from other technical lignins, as they
have low molecular weight and high chemical purity and relatively
narrow molecular weight distribution, see Section 2. The organosolv
lignins that have high solubility in organic solvents are more hydropho-
bic and show poorer solubility in water [42]. Progress in the lignin
organosolv field is scattered, as the paper by Pereira et al. demonstrates,
in which an organosolv-CO2 supercritical pulping process for the lignin
extraction [43] or dissolved air flotation (DAF) as an effective method of
recovering organosolv lignin precipitates. DAF is used to avoid precipi-
tating or the use of collecting agent, in which case low temperature is
important for the precipitate formed to attach to the micro-bubbles
[44]. Sano and co-workers [45,46] used purified organosolv lignin for
carbon fibers, and further development of carbon fibers from
organosolv lignin was taken by Kadla et al. [47]; see more details in
Section 4.1.
3.2. Lignin surface chemistry
As mentioned earlier, it is difficult to describe lignin with a defined
repeating monomer unit connected in an uniform way. Furthermore,
as solid state lignin is amorphous due to the irregular branching and
molecular weight of the biomacromolecules, structural heterogeneity
also persists [48•]. Obviously, significant problems arise in the study of
the fundamental physicochemical properties of lignin. Partly, this has
been overcome by the preparation of model lignin surfaces closely
mimicking the naturally occurring material; however, it was overcome
with the reduction or elimination of the chemical and structural hetero-
geneity. To achieve this, well-characterized lignins, either isolated from
naturally occurring materials or synthesized, have to be used in the
preparation of thin films.
Model films of lignin have been prepared by a number of research
groups for use in the measurement of fundamental properties of lignin
in the solid state, using a different methodology, however, bearing in
mind the underlying goals of achieving chemical and structural
uniformity [49–70].
The first model films were prepared by Lee and Luner in investigating
the wettability and interfacial properties of lignin [49]. The surfaces in
this study were prepared either by evaporation of a drop of lignin
solution on a microscope slide, resulting in extensive cracking, or
through heat molding of the lignin powder under pressure to give
412 M. Norgren, H. Edlund / Current Opinion in Colloid & Interface Science 19 (2014) 409–416
smoother surfaces. However, films prepared in this manner are far from
ideal for the calculation of surface energy.
Constantino et al. [50•–52] used the Langmuir–Blodgett technique to
prepare model lignin films, and they later used them in sensor
applications for heavy metal detection [53•]. Micic et al. investigated
the use of model lignin macromolecules in determining the interactions
between lignin globules [54•,55]. Norgren and co-workers prepared
smooth, continuous lignin films by spin-coating several different lignin
derivatives dissolved in ammonium hydroxide solution onto oxidized
silicon wafers [59•–64]. Thicknesses in the range of 30–150 nm with
minimum roughness as demonstrated by the atomic force microscopy
imaging have been reported (Fig. 3). Importantly, the lignin films re-
main intact upon exposure to a range of aqueous solution conditions.
A key property of lignin that has been quantified by the preparation
of lignin films is its surface energy and wettability. The surface energy of
lignin is highly dependent on a number of factors, not least the method
of evaluation, the isolation of the polymer from the wood, the tree spe-
cies and the surface preparation. In the pioneering studies of Lee and
Luner briefly mentioned before, they prepared six different lignin prep-
arations and observed no significant differences in their wetting charac-
teristics [49]. Recently, Notley and Norgren have undertaken a similar
study investigating the differences in the surface energy components
between kraft lignin films and milled wood lignin films determined by
measuring contact angles with test liquids of varying polar and disper-
sive components according to the method of Fowkes [60••]. The surface
energy was in the range 53–56 mJ m−2 for the milled wood lignin films
and the kraft lignin film. The polar component of the surface energy was
found to be significantly higher for kraft lignin than for milled wood lig-
nin due to an introduction of charged chemical groups by the chemical
reactions occurring from harsh conditions in the isolation process from
wood. Interestingly, the surface energy of all lignin samples was deter-
mined to be remarkably similar to that of cellulose, the other major
components in the wood cell wall.
The interaction of lignin with other materials has also been studied
extensively. One example is the surface forces between lignin and cellu-
lose [61•]. Tammelin et al. have used model lignin films to investigate
the interaction of hemicellulose and extractives with lignin [65].
Hollertz et al. recently presented a quantitative estimate of the
dispersive interactions between, lignin, hemicelluloses and cellulose
and determined the non-retarded Hamaker constant for lignin's
interactions with the other wood polymers [66•].
Fig. 3. AFM non-contact mode height image of a kraft lignin thin film prepared by spin-
coating. Film thickness 55 nm, scanning area 5.0 × 5.0 μm2, RMS roughness 1.01 nm.
Adapted with permission from Norgren et al., Langmuir 2006; 22:1209-14.[59] Copyright
(2006) American Chemical Society.
Lignin model films have been used to study the adsorption of poly-
electrolyte complexes and polyelectrolytes in terms of both the kinetics
and surface excess under variable solution conditions such as pH, ionic
strength and polymer concentration [62•,63•]. Recently, physical vapor
deposited thin films of lignins extracted from sugar cane bagasse were
prepared in order to explore basic properties such as electrical and
surface morphology and the sensing performance of these lignins as
transducers [69]. The authors showed by e.g. impedance spectroscopy
that the film could be used to sense aniline vapor.
Model films also provide an excellent opportunity to study the
properties of single-lignin macromolecules. This may be probed by
stretching lignin polymers away from the surface by some specific
physisorption interaction with an atomic force microscopy tip in a
method that has been termed single molecule force spectroscopy
[70,71]. Only a few polymer chains are pulled away from the surface,
with each chain causing an “event” that can be observed in the force–
distance curve [72].
4. On the development of lignin into high-value materials
The efforts in using lignin derivatives in more sophisticated applica-
tions are currently booming. Society's need to replace oil-based and
non-renewable surface active and polymeric materials is the main driv-
ing force. As a set of examples, lignins are being used for the controlled
release of fertilizers, modified for slow-release fertilizers and herbicides
in agriculture [73–75], as a base for different materials application in the
fields of bioplastics [75–77], (nano)composites [76–79] and nanoparti-
cles [80–84]. Furthermore, as adsorbents in solution [85–91], protective
UV-absorbents [67,68], dispersants [29,32•–36,92–94], to improve
the saccharification of lignocelluloses in the production of biofuels
[95–98], in electro-chemical applications [99–102] and in environmen-
tal friendly functionalization approach to extend the role of lignin for
future biomass and biofuel applications [103•].
Lignins are used in controlled-release formulations as in thin coating
layers of urea granules [73] or as microcapsules of herbicides formed by
the layer-by-layer self-assembly method [74]. The release rates from the
microcapsules of herbicides could be controlled by the number of self-
assembly layers, and the results demonstrated that it could be a
promising approach for the controlled release of other herbicides and
pesticides.
Recently, kraft lignin has been used for microcapsulation processes
assembled by ultrasound into lignin microcapsules (LMC) for the
storage and delivery of hydrophobic molecules [83]. The mechanism
responsible for the formation of LMC is a combination of two
ultrasound-induced phenomena: emulsification and cross-linking.
Tortura et al. discuss the capsule formation highlighting the physico-
chemical characteristics as the abundance of phenolic groups, high mo-
lecular weight, hydrophobic interactions within the oil phase and a
distinct solubility in alkaline conditions.
Adsorption of multivalent ions on lignin and different new lignin-
containing materials as biocomposites, nanocomposites, biosorbents
and hydrogels has been of recent interest. The focus is on the strong
chelation and removal of different multivalent ions, e.g., from waste
waters [85–91]. Lignin's UV-absorbing properties have been utilized in
surface treatment of fabrics with lignin nanoparticles, and the treated
fiber surfaces also showed antibacterial and antistatic properties [67,
68]. In the field of dispersants, the focus significantly differs, but both
kraft lignin and lignosulfonates are used as lignosulfonates for TiO2-
particles and graphene nanosheets [29,93••] and kraft lignin for carbon
nanotubes and recyclable emulsifiers.[92,94]. To enhance enzymatic
saccharification of lignocelluloses the use of lignosulfonates is shown
to be an efficient process parameter. The process efficiency is affected,
and higher hydrolysis pH, low molecular weight and good sulfonation
can enhance enzymatic saccharification of pure cellulose [95–98].
Inganäs and co-workers made thin films from the mixtures of lignosul-
fonates from black liquor and pyrrole. Interpenetrating networks of
 M. Norgren, H. Edlund / Current Opinion in Colloid & Interface Science 19 (2014) 409–416
lignosulfonates and the conjugated polymer, polypyrrole and, pyrrole
are synthesized by galvanostatic polymerization in an acidic aqueous
electrolyte. The film is used as the cathode in batteries, particularly
cheap batteries that should be able to store energy from solar cells
and wind turbines [100••,101]. Crestini et al. discuss a new environmen-
tally friendly approach for the functionalization of lignin and lignin
model compounds in the light of exploiting biocompatible material for
the development of novel value-added biorefinery streams. Two
strategies are highlighted in the paper: a selective functionalization of
the lignin polymer and an oxidative depolymerization to acquire
polyfunctional monomeric compounds [103•].
4.1. Lignin as a potential carbon fiber precursor
Today, the most important starting material for carbon fiber produc-
tion is polyacrylonitrile (PAN), but due to high costs, these carbon fibers
remain a niche product for use in high-end industrial applications,
aerospace, sporting equipment and different luxury automotive prod-
ucts [104]. However, in the recent times, the interest in lignin for its
use as an inextensible raw material for the production of carbon fibers
of reasonable qualities is rapidly growing [105•,106••]. Of course, the
rate of success for this still relies on the fundamental knowledge of
lignin's physical chemistry, which has been reviewed in earlier sections.
Already in the late 1960s and the beginning of the 1970s, the first
patents and reports on the production of carbonized material from lig-
nin were mentioned, and the production methods were dry and wet
spinning using an alkali-modified lignin solution [107–109]. A renewed
interest in the beginning of the 1990s occurred when Sudo et al. pre-
pared carbon fibers from steam-exploded lignin, modified through
hydrogenolysis and phenolysis, which had a very good spinnability in
the melt state [110,111], and then later when Sano and co-workers
[45,46] applied melt-spinning on purified organosolv lignin. A further
step in the development was taken by Kadla et al., who investigated
kraft and organosolv lignin as well as lignin blends [47]. The increasing
popularity of lignin-derived carbon fibers is discussed more extensively
by Frank et al. [112,113••] and Baker and Rials [114••].
Advantages of using lignins as precursors to carbon fibers are related
to the high carbon content and high carbon yield after carbonization
and the lack of exposure toxic elimination products during carboniza-
tion. Furthermore, the accessibility of lignin in large quantities could
push the development of inexpensive, carbon-fiber, light-weight mate-
rials. Frank et al. [113••] also reviewed the life cycle assessment by Das
[115], comparing different carbon-fiber precursors and manufacturing
processes, and as we discussed, the outcome indicated that lignin is
the best carbon-fiber precursor.
Fig. 4. (a) SEM micrographs of ALCFPt 900 (scale bar: 1 μm) Reprinted from Carbon, Vol. 48, Ruiz-Rosas et al., The production of submicron diameter carbon fibers by the electrospinning of
lignin, 696–705 [117], Copyright (2010), with permission from Elsevier. (b) 70/30 lignin/PVA composite nanofiber mat from 12 wt.% aqueous solution. The inset in the image depicts the
corresponding optical photo of a mat (with size of 2.5 × 5 cm). Reprinted from J. Power Sources, Vol. 247, Lai et al., Free-standing and mechanically flexible mats consisting of electrospun
carbon nanofibers made from a natural product of alkali lignin as binder-free electrodes for high-performance supercapacitors, 134–141 [122], Copyright (2014), with permission from
Elsevier.
413
Carbon nanofibers with diameters as small as 200 nm have been suc-
cessfully prepared from lignin using electrospinning [116•]. Ruiz-Rosas
et al. [117] synthesized lignin fibers in a single-step procedure utilizing
electrospinning (Fig. 4a). In a recent study, nanofiber mats with smooth
surfaces and without defects were produced from a softwood kraft
lignin feedstock purified by solvent extraction prior to electrospinning
[118]. The structural alignment of the lignin-based carbon fiber mats
was found to be of great importance in further improving the mechan-
ical strength of the material [119].
It has been shown that the stabilization and carbonization of kraft
lignin fibers for carbon fiber production can be performed as a one-
step process, differing merely in temperature and treatment time.
These findings have great potential to reduce the processing costs in
future commercialization of lignin as a raw material for carbon fibers
[120•]. Also the electrospinning of technical lignins for the production
of fibrous networks has been performed (Fig. 5) [121]. It is envisioned
that the mechanically flexible mats of carbon nanofibers made from
alkali lignin would be innovative and sustainable electrode materials
for flexible high-performance supercapacitors (Fig. 4b) [122]. Taking a
different approach, Saha et al. synthesized mesoporous carbon from
lignin gels in a recent study using structure-dictating agents to control
porosity in a supercapacitor electrode material [123].
The scientific discussion is recently focused on issues related to
surface and colloid chemistry also in this field. Baker et al. [124]
manufactured high-strength lignin-based carbon fibers addressing
the glass-transition temperature, molecular weight and molecular
weight distribution as the key parameters in the production, using
solvent fractionation to provide pure softwood kraft lignin. To produce
polymeric materials from lignin in an orderly manner, Spender et al.
[125] used ice-segregation-induced self-assembly that relies on lignin
self-aggregation during unidirectional freezing. Although this tech-
nique is not a future large operation, it shows the emerging field of in-
teresting new ideas within the field.
5. Conclusion and outlook
In this review, we have tried to summarize the current knowledge
and ongoing efforts to increase the potential use of the under-utilized
resource lignin. In spite of its abundance and due to its complexity, it
should be pointed out that in comparison to other biopolymers, lignin
has still not been sufficiently described from a physicochemical point
of view. With increasing global demands on lowering the carbon
dioxide emissions and the inevitable rise in the cost of oil and
petroleum-based chemicals, it is obvious that biomass will play a
pronounced role in providing for future economic prosperity. Lignin,
414 M. Norgren, H. Edlund / Current Opinion in Colloid & Interface Science 19 (2014) 409–416
Fig. 5. SEM images of 95:5 and 99:1 softwood kraft lignin:PEO fibers electrospun from solutions at different concentrations. (a): 95:5, 20 wt.%, (b): 95:5, 25 wt.%, (c): 95:5,
30 wt.%, (d): 99:1, 30 wt.%, (e): 99:1, 35 wt.%, (f): 99:1, 40 wt.%. Scale bar: 20 μm. From [121]; Electrospinning of technical lignins for the production of fibrous networks, Dallmeyer
et al., Journal of Wood Chemistry and Technology, Nov. 20, 2010, Taylor & Francis Ltd., reprinted by permission of the publisher.
already available in large volumes as a by-product of the pulping indus-
tries, could fill a part of this function. Besides the transformation of lignin
into different fine chemicals and liquid fuels, which are not covered and
out of the scope of this review, and the many different possible uses of
lignins exemplified in Section 4, we find the development of carbon fi-
bers of various dimensions and different applications based on such
structures to be among the most promising approaches toward large-
scale production of high-value materials so far. The academic interest
in this specific area, quantified as the annual increase in the number of
publications, has also grown significantly [113••]. If lignin can be pro-
duced with a more constant structure and size in dedicated biorefineries,
its potential for exploitation and utilization in future high-value products
also beyond carbon fibers will probably be greatly improved.
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