i n d u s t r i a l c r o p s a n d p r o d u c t s 2 7 ( 2 0 0 8 ) 202–207

available at www.sciencedirect.com

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

Lignin as a base material for materials applications:

Chemistry, application and economics

Derek Stewart ∗
Scottish Crop Research Institute, Quality and Health Programme, Dundee DD2 5DA, Scotland, UK

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

Keywords: Lignin has long laboured under the label of “waste material”. However, as part of the the-
Lignin matic network EUROLIGNIN, a survey and desk study was undertaken to assess the changes
Economics and patterns in the utilisation of lignin with respect to materials applications. This showed
Feedstock that over the last 10–15 years there has been an explosion of research into, and commer-
Sector cialisation of, lignin-based products and processes which add significant value to a material
Polymer composites that was previously, and continues to be, used as a low-value fuel for pulping boilers. The
innate chemistry of lignin, a phenolic heteropolymer, has allowed it to make inroads into
the high value polymer industries whilst continuing to act as feedstock material for the
binder industries. Indeed the replacement of phenolics by lignin in resins systems is eco-
nomically attractive with the phenolic resins market utilising approximately 2.52 M tonnes
in 2001. Currently lignin, predominantly as lignosulphates, is used as a binding and dis-
persing agent in different industries with approximately 1 M tonnes (on a 100% solids basis)
used annually, for example, in concrete admixtures. These and other applications will be
discussed and expanded upon here with emphasis on both the economics of the markets
and what is still required for lignin to mature as a valuable resource in its own right.
© 2007 Elsevier B.V. All rights reserved.

1. Introduction no longer necessarily as chemically heterogeneous as they

Traditionally lignin has been viewed as a waste material or a
low value by-product of pulping with its utilisation predom-
inantly limited to use as a fuel to fire the pulping boilers.
Indeed it has been estimated that only 1–2% of lignin is iso-
lated from pulping liquors and used for speciality products
(Lora and Glasser, 2002). This mindset is still with us today in
the modern approaches to fuel generation, such as the con-
version of biomass into ethanol, where the residual lignin
is used as a fuel for power generation to drive the fermen-
tative ethanolification (Hamelinck et al., 2005). The time is
now ripe to change this view as a result of several factors.
Advances in specific chemical processing have meant that
the lignins produced either by pulping or other means are
previously were. Also the chemical industries are broaden-
ing their end user markets leading to requirements for a
feedstock base that can meet the needs of these new end prod-
ucts and imbue them with novel properties. In addition, the
increasingly stringent environmental waste regulations, both
at the national and European level, mean that all wastes must
be dealt with and the diverse chemical moieties inherent in
lignins from diverse plant sources and processing/extraction
methods mean that it should profit from this via purification,
processing and integration into new and established chemi-
cal industry subsectors such as polymers, resins, adhesives,
etc. The aim here is to show how lignin has or can become
integrated into these materials industries and to highlight
blossoming lignin research that can use lignin as a novel and

∗
Tel.: +44 1382 568517; fax: +44 1382 562426.
E-mail address: Derek.Stewart@scri.ac.uk.
0926-6690/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2007.07.008
 i n d u s t r i a l c r o p s a n d p r o d u c t s 2 7 ( 2 0 0 8 ) 202–207
appropriate, renewable feedstock rather than as a replace-
ment for synthetic phenolics.
Due to the enormity of the task, the study of lignin
in materials applications will be subdivided into specific
subsectors although there is some overlap between these:
phenolic resins, epoxies, adhesives, polyolefins and miscel-
laneous. The latter is a “catch all” category, which contains
the non-specific and novel applications. For each subsector
specific examples are highlighted and, where available, the
economic case is presented for the adoption of lignin or lignin-
derived chemicals into that field. This review does not pretend
to be comprehensive. Rather it seeks to be a broad-brush
approach over the potential applications and development
of lignin into an important chemical feedstock in its own
right.
1.1. Phenolic resins
Lignin should be an obvious candidate for application as a phe-
nol substitute in phenol formaldehyde resins but its chemical
heterogeneity is the limiting factor and, at an additive level of
5–10% of the resin weight, has led to the production of resins
with increased Mw (Turunen et al., 2003). This can be countered
however via several avenues:
• (Bio)chemical modification of the lignin. Reaction with
enzyme systems to oxidatively crosslink the lignin (Popp
et al., 1991) or pre-reaction of the lignin with methylolated
phenols increased its reactivity (Doering, 1993). Pre-reaction
of the lignin and the phenol prior to the introduction of the
crosslinker, formaldehyde, has also been reported (Ludwig
and Stout, 1972; Lai, 1996).
• The addition of filler agents. Peng and Riedl (1994) used
starch as a filler in phenol–formaldehyde thermoset resins
and found that p–p bridge structures (with respect to the
phenolic C1 ) were enhanced with lignosulphate as the lignin
source. In addition, when starch derived from wheat was
used, it produced the lowest level of condensation resulting
in the highest reactivity of the lignin–starch combinations
to formaldehyde.
• Employing novel process derived lignins. Lignins derived
from acetosolv (Vázquez et al., 1999), acid hydrolysis (Sellers
et al., 1994a) and organosolv processes (Sellers et al., 1994b,
c; Cetin and Ozman, 2002) were shown to be effective
phenol diluents in phenol-based resin systems. For exam-
ple, the use of acetosolv lignins in phenol–formaldehyde
resin and subsequent plywood board formation produced
board knife-test results better than those obtained with
a commercial phenol–formaldehyde resin (Vázquez et al.,
1999). Similarly, Cetin and Ozman (2002) showed that
the direct replacement of organosolv lignin for phenol in
phenol–formaldehyde resins exhibited satisfactory resin
properties and had good curing properties compared to the
lignin free resin.
On a purely economic basis the introduction of lignin to
the phenolics market is credible. Global production of phe-
nol is almost exclusively based on the cumene-based acetone
co-product process (98% in 2005; Anon, 2006) and produced
∼8.25 M tonnes in 2004 of which 30.6% went for use as pheno-
203
lic resins. The whole phenol production output was valued at
approximately $107 billion and predictions for the future sug-
gest that the current ∼1380 D /tonnes price is set to increase
along with the predicted annual demand (Anon, 2004a, 2006).
In addition the increasing legislation surrounding waste and
effluent management along side the push to use renewable
materials mean that the employment of lignin in this filed is
eminently logical.
1.2. Epoxies
The use of lignin in this resin field is one of adjunct crosslinker
within the normal classic epichlorohydrin reaction wherein
lignin would impart the bulk properties. For these applications
the lignin must be impurity free, i.e. free of salts, water and
sugars. This can be achieved by purifying waste lignins (pre-
cipitation, deionisation, etc.) derived from the common pulp
and paper processes (Kraft, Soda, etc.) or direct use of lignin
from the less condensing pulping processes such as Alcell,
non-wood fibres pulping.
There have been several developments and reports
focussed on lignin–epoxy developments (see Simionescu et al.,
1993) but perhaps the most novel is that of its use in printed
circuit boards (Kosbar et al., 2001). In 2001, research carried out
at IBM was published wherein lignin was incorporated into
the resin for fabrication of printed circuit boards. This resin
had physical and electrical properties similar to those of com-
mon laminate resins (Kosbar et al., 2001). Currently the scale of
operation is somewhere between the patent (Afzali-Ardakan
et al., 1998, 2002) and development scale stage.
Conversely, the production of lignin–epoxy resins for
moulded composites encompasses the laboratory to indus-
trial scale with the Lenox® lignin–epoxy resins being produced
at ∼350 kL/annum at their peak prior to liquidation of the
company in 2000. Similarly, the studies of Cazacu and Popa
(2003) and Simionescu et al. (1993) have shown that epoxy-
modified lignin-based resins can be prepared in significant
quantities (∼0.5 ML/annum) via relative simple purification
schemes involving reacting the lignin with epichlorohydrin
and subsequent reclamation of the unused epichlorohydrin
and filtration to purify the ultimate resin. Moreover studies by
Simionescu et al. (1993) showed that significant lignin loads
(<50%, w/w) could be incorporated into the epoxy resin whilst
still maintaining good electrical (volume and surface resis-
tivity, dielectric constant, loss in dielectric tangent angle and
dielectric rigidity) and mechanical properties, and high impact
toughness (Charpy impact strength) compared to the lignin-
free phenol epoxy resins.
The origin and subsequent extraction/processing of the
lignin has a distinct effect on the ultimate properties of the
composite. Epoxy–lignin blends derived from different lignin
types showed that those blends containing hardwood lignin
(TomliniteTM and EucalinTM ) separated by the Kraft process or
isolated by steam explosion crosslinked more efficiently than
those derived from softwood lignin (Indulin AT; Simionescu et
al., 1993). It was concluded that the disparity in performance
was derived from the difference in chemical structural and
molecular weight.
The epoxide resin market is a economically vibrant
and, with specific reference to phenol–epoxy resins, one in
204 i n d u s t r i a l c r o p s a n d p r o d u c t s 2 7 ( 2 0 0 8 ) 202–207
which lignin could flourish as a crosslinking agent (Anon,
2004b). In 1999, the estimated value for epoxy resin pro-
duction in the United States, Western Europe and Japan
was over $2 billion. The 7–10% average annual growth
rates of the 1970s have slowed considerably with future
growth of epoxy resin consumption in the United States
and Western Europe averaging about 3.5–4% per annum
from 1999 to 2004. The three leading producers of epoxy
resins are Hexion (formerly Shell’s Epoxy Resins and Reso-
lution Performance Products), Dow and Huntsman. Together
they account for approximately 75% of the world’s capac-
ity. Given that the market is expanding, and continues to
do so in the mid to long term, there will be distinct oppor-
tunities for lignin especially as its inherent properties, also
reflected in the end product, are studied and characterised in
more detail.
1.3. Adhesives
The principle point of entry for lignin in the adhesives sub-
sector is likely to be in fibreboard production. Technologies
have been trialled by Lund et al. (2000) and Felby et al. (2002,
2004) wherein the in situ crossreaction of lignin via laccases
(oxidoreductases) were used at the pilot plant level to pro-
vide boards comparable in strength to those produced using
urea–formaldehyde adhesives. The inclusion of hot pressing
to this process further increased the crosslinking. Moreover,
solubilisation of lignin in PF glue (30%, w/w) led to increases
in plywood shear strength.
Gel permeation experiments following the in situ treatment
of lignin in beech fibres with laccase showed distinct increases
in molecular weight of the lignin directly supporting the sug-
gestion that lignin covalent inter-bonding was occurring (Felby
et al., 2002). In addition, model compound studies (Bohlin et
al., 2005) have shown that the laccase treatment of lignin
model compounds (and by inference lignin) generates moi-
eties of increasing molecular weight that can react further to
increase crosslinking (Fig. 1).
The fibreboard market has a large turnover but operates
on a low-profit margin and this makes the introduction of
new technologies notoriously difficult (Anon, 2003). However,
fibreboard production is predicted to increase from 15.4 to
16.8 Mm3 over the period 2002–2006, an 8.3% increase. Given
the increasing legislation surrounding the restriction of chem-
ical usage in fibreboard formation it is likely that alternative,
safer sources will be sought and the laccase system should
benefit from this.
Fig. 1 – Laccase-mediated oxidation of lignin model compound and putative further reaction leading to lignin crosslinking.
1.4. Polyolefins
The polyolefin (PO) subsector may be a welcome home for a
lignin feedstock and it would integrate via polymer blends and
UV stabilisation as reflected in the studies of Cazacu et al.
(2004a,b) and Gosselink et al. (2004), respectively. There are
conflicting reports regarding the benefits of lignin incorpo-
ration into polyolefin blend polymers. Gonzales-Sánchez and
Espósito Alvarez (1999) found that the incorporation of Kraft
lignin into polypropylene (PP) was accompanied by poor adhe-
sion between lignin and PP whilst others found that there
was a reduction of the physico-mechanical properties with
increased levels of lignin (Rusu and Tudorachi, 1999; Tudorachi
et al., 2000a,b). However, more modest levels of lignin incor-
porations provided polymers with acceptable or improved
performance characteristics. For example, incorporation of
epoxy-modified lignosulfonate into a binary polyolefin mix-
ture (70 PP/30 polyethylene (PE)) at levels of 2.5–40% (w/w) gave
blended polymers with good thermal, physico-mechanical
and surface properties (Feldman et al., 1995). Furthermore, the
blends of Kraft and aminated lignins with PP or PE, respec-
tively produced polymers with improved strength, elongation
at break and other elevated mechanical indices (Wang et al.,
1992; Simionescu et al., 1996).
With regard to polyolefin polymer UV stabilization, the
lignins (NovaFiber and Kraft) utilised by Gosselink et al. (2004)
were comparable to a common, but relatively expensive, com-
mercially applied stabiliser (Hindered Amine Light Stabiliser,
HALS). In this case the price benefit should drive the commer-
cial uptake of lignin.
An increasingly important factor surrounding plastics in
general but specifically polyolefin-based products is that of
their recalcitrance to biodegradation. However, this is one area
where there are significant benefits to be had by the incorpo-
ration of lignin. Variation of the degree of lignin incorporation
is reported to be accompanied by increases in the degree and
rate of biodegradation (Simionescu et al., 1996; Tudorachi et
al., 2000a,b; Rusu and Tudorachi, 1999).
The global market for polyolefins is enormous with PE and
PP representing roughly 60% of all the thermoplastics pro-
duced and sold in the world with an associated large economic
value (Anon, 2004a). For example, a subsector of this, low-
density polyethylene, continues to be a large global business
with an estimated 2001 value of $19 billion. Global demand
for all types of PE exceeded is projected reach 63.4 M tonnes in
2006 (Anon, 2004a). Polypropylene (PP) resins are another fast-
growing category with a predicted consumption of 38 M tonnes
 i n d u s t r i a l c r o p s a n d p r o d u c t s 2 7 ( 2 0 0 8 ) 202–207
in 2005 representing a value of approximately $42 billion
(Anon, 2004a). It is predicted that as developing countries shift
from a largely agrarian to an industrial economy, there will
be growth opportunities for PP to substitute for paper, metal,
wood, glass and natural fibers and it is unthinkable that given
the distinctive properties associated with lignin that some
inroads cannot be made into this market especially by the
blended polymer approach leading to products with unique
characteristics directly attributable to the source lignin.
1.5. Miscellaneous
This subsector contains all the lignin utilisations not readily
categorised as above. Lignin utilisations have been reported
relating to a multitude of applications. For example they have
been reported to be useful as binders in mortar and con-
struction systems, metal sequestration in solutions and in
vivo, biodegradable plastic additive, basis of gel formation,
polyurethane copolymers, etc. (Nadif et al., 2002; Crist et al.,
2003; Baumberger, 1999; Nishida et al., 2003; Kelley et al., 1989;
Yoshida et al., 1987). These are only a few examples of the
huge number of ways in which lignin have been used for very
diverse end uses. Given the diversity of these applications
and the processes involved the requirements of the source
lignin are equally broad. The binder and agglomeration uses
are simple solid–solid dispersions with the lignins aiding by
maintaining and affecting fluidity as a result of lignin–lignin,
lignin–water interactions. Metal sequestration is based on
phenolic-metal ion attraction and has been commercialised in
one form as LIGNORTM (Zhuang and Walsh, 2004), a treatment
for acid rock drainage. In this application ligninsulphontaes
are used to protect lime from developing an external surface
coating by sequestering/chelating metal ions. Furthermore,
metal sequestration can be enhanced by modifying the lignin
with amino and quaternary ammonium groups (Dizhbite et
al., 1999). As with almost all the previously discussed applica-
tions of lignin the end properties are dependent on the source
and purity of the lignin. Generally, the less heterogeneous the
lignin the fewer problems are found in the application and/or
the more specific the properties of the end product. This may
be due to removal of impurities or simply that the lignin is less
chemically and structurally heterogeneous and therefore will
behave in a more uniform manner throughout any subsequent
processing.
Besides the more mainstream applications of lignin there
are some more unique ones that may, in the long term, exhibit
the properties unique or exemplary enough to commercialise
lignin effectively. For example, studies by Dizhbite et al. (1999)
have shown that the amination of lignin with epoxy amines
enhanced its sorption activity towards heavy metals and this
also enhanced the sorption capacity for bile acids and choles-
terol. Nishida et al. (2003) prepared lignin gels from acetic
acid lignin by crosslinking with polyethylene glycol diglycidyl
ether. These gels are the first to exhibit swelling behaviour
in aqueous ethanol solution, in particular 50% (v/v) solu-
tion. In addition, they also swelled in alkaline solution and
shrank upon heating. This unique ability means that further
tailoring of the lignin may allow the gel to sequester com-
ponents in mixed solvent systems, an hitherto unattainable
goal.
205
With regard to the economics for this very diverse category,
the largest markets for both the evaporated lignin concen-
trate and the spray-dried lignosulfonates are as road binders.
In 2001, apparent world consumption of lignosulfonates was
about 1 M tonnes on a 100% solids basis. Concrete admix-
tures accounted for the majority of use in most of the world
(about two-thirds of use in Japan). Over the next 5 years, the
consumption of lignosulfonates for this use is expected to
decline slightly in Japan and the United States due to refined
construction techniques and reduced demand for concrete,
grow sluggishly in Western Europe, moderately in Canada,
and strongly in the rest of the world, particularly in China.
Overall, global consumption is expected to decline slightly,
by less than 0.5% (Anon, 2004c). Metal ion sequestration is
most likely to be the avenue, which will boom in the mid
to long term as waste and effluent regulations continue to
increase but economic values for this are almost impossible to
obtain due to the lack of clear definitions. This becomes even
more difficult to ascertain in the newer markets such as lignin
gel, etc.
2. Conclusions
Clearly utilisation of lignin in the material industries sector
is limited only by the imagination. Its uses are diverse and
multiple and this attempt to try and define some subsectors
has only skimmed the surface. The future for the applica-
tion, development and commercialisation of lignin is assured
if effort is rationalised and concentrated into critical mass in
specific key areas. From a purely economic perspective the
development of lignin in the polyolefins sector merits a much
more detailed study given the vast financial sums involved
in the PE and PP markets and the benefits with regard to
biodegradation that lignin could potentially bring. Indeed, this
approach of selecting the most viable example for each sec-
tor for a much more detailed study would act as an excellent
example for a broad swath of applications. Supplemented with
the relevant literature, patent applications and in depth dis-
cussion with the appropriate key players in the marketplace
such a report would go a long way to make the case for the
further promotion of lignin as a utilitarian and necessary feed-
stock for the chemical industries.
Acknowledgements
The author thanks the following for support: Commission of
the European Communities, Directorate-General for science,
research and development & the Scottish Executive Environ-
ment and Rural Affairs Department. This paper is a direct
output from EUROLIGNIN (G1RT-2002-05088) and the author
thanks the project managers Drs. Ed De Jong and Richard Gos-
selink.
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