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 LIGNIN IN POLYMER
COMPOSITES

Omar Faruk
Mohini Sain

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understanding, changes in research methods, professional practices, or medical treatment may become necessary.
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 Dedicated
to
My Beloved Wife
“Shaila Shumi”
and
My Beloved Daughter
“Ornela Suhiya”

Omar Faruk, Canada


Umesh P. Agarwal USDA Forest Service, Forest
Products Laboratory, One Gifford Pinchot Drive,
Madison, WI, USA
Abdullah Al Mamun Institute for Materials
Engineering, Polymer Engineering, University of
Kassel, Kassel, Germany
Priyanka Bhattacharya Proton Power, Inc., Lenoir
City, TN, USA
Sabornie Chatterjee Chemical Sciences Division,
Oak Ridge National Laboratory, Oak Ridge,
TN, USA
Hoyong Chung Department of Chemical and
Biomedical Engineering, Florida State University,
FAMU-FSU College of Engineering, Tallahassee,
FL, USA
Norbert Eisenreich Fraunhofer-ICT, Germany
Gunnar Engelmann Fraunhofer Institute for
Applied Polymer Research IAP, Potsdam-Golm,
Germany
Omar Faruk Centre for Biocomposites and
Biomaterials Processing, Faculty of Forestry,
University of Toronto, Toronto, ON, Canada
Maik Feldmann Institute for Materials
Engineering, Polymer Engineering, University of
Kassel, Kassel, Germany
Johannes Ganster Fraunhofer Institute for Applied
Polymer Research IAP, Potsdam-Golm, Germany
Azadeh Goudarzi Department of Materials
Engineering, The University of British Columbia,
Vancouver, BC, Canada
Shayesteh Haghdan Department of Wood Science,
Forest Sciences Centre, The University of British
Columbia, Vancouver, BC, Canada
Hans-Peter Heim Institute for Materials
Engineering, Polymer Engineering, University of
Kassel, Kassel, Germany
Contributors
Emilia Regina Inone-Kauffmann Fraunhofer-ICT,
Germany
John F. Kadla Department of Forest Biomaterials,
North Carolina State University, Raleigh, NC, USA
Adel R. Kakroodi Centre for Biocomposites and
Biomaterials Processing, Faculty of Forestry,
University of Toronto, Toronto, ON, Canada
Muzaffer A. Karaaslan Department of Materials
Engineering, The University of British Columbia,
Vancouver, BC, Canada
Simon Kleinhans Institute for Materials
Engineering, Polymer Engineering, University of
Kassel, Kassel, Germany
Frank K. Ko Department of Materials Engineering,
The University of British Columbia, Vancouver, BC,
Canada
Mark T. Kortschot Department of Chemical
Engineering and Applied Chemistry, Advanced
Materials Group, University of Toronto,
Toronto, ON, Canada
Yingjie Li Department of Materials Engineering,
The University of British Columbia, Vancouver, BC,
Canada
Li-Ting Lin Department of Materials Engineering,
The University of British Columbia, Vancouver, BC,
Canada
Helmut Naegele Tecnaro GmbH, Germany
Mohammad Ali Nikousaleh Institute for Materials
Engineering, Polymer Engineering, University of
Kassel, Kassel, Germany
Numaira Obaid Department of Chemical
Engineering and Applied Chemistry, Advanced
Materials Group, University of Toronto, Toronto,
ON, Canada
Nikhil D. Patil Faculty of Forestry, University of
Toronto, Toronto, ON, Canada
xiii
xiv C ONTRIBUTORS

Juergen Pfitzer Tecnaro GmbH, Germany Nicolas R. Tanguy Faculty of Forestry, University
of Toronto, Toronto, ON, Canada
Scott Renneckar Department of Wood Science,
Forest Sciences Centre, The University of British Jimi Tjong Centre for Biocomposites and
Columbia, Vancouver, BC, Canada Biomaterials Processing, Faculty of Forestry,
University of Toronto, Toronto, ON, Canada
Annette Rüppel Institute for Materials
Engineering, Polymer Engineering, University of Newell R. Washburn Department of Chemistry,
Kassel, Kassel, Germany Carnegie Mellon University, Pittsburgh, PA,
USA; Department of Biomedical Engineering,
Mohini Sain Centre for Biocomposites and
Carnegie Mellon University, Pittsburgh,
Biomaterials Processing, Faculty of Forestry,
PA, USA
University of Toronto, Toronto, ON, Canada; Centre
of Advanced Chemistry, Adjunct, King Abdulaziz Ning Yan Faculty of Forestry, University of
University, Jeddah, Saudi Arabia Toronto, Toronto, ON, Canada; Department of
Chemical Engineering and Applied Chemistry,
Tomonori Saito Chemical Sciences Division, Oak
University of Toronto, Toronto, ON, Canada
Ridge National Laboratory, Oak Ridge, TN, USA
Daniel J. Yelle USDA Forest Service, Forest
Viola Sauer Institute for Materials Engineering,
Products Laboratory, One Gifford Pinchot Drive,
Polymer Engineering, University of Kassel, Kassel,
Madison, WI, USA
Germany
Lars Ziegler Tecnaro GmbH, Germany
Gregory D. Smith Department of Wood Science,
Forest Sciences Centre, The University of British
Columbia, Vancouver, BC, Canada
Nicole M. Stark USDA Forest Service, Forest
Products Laboratory, One Gifford Pinchot Drive,
Madison, WI, USA
 Editor’s Biography
Omar Faruk Mohini Sain
Dr Omar Faruk Mohini Sain is
completed his BS and dean and professor at
MS in chemistry at Faculty of Forestry,
the University of Chit- University of Toronto.
tagong, Bangladesh. He specializes in ad-
With a DAAD vanced nanocellulose
(German Academic technology, biocom-
Exchange Service) posites, and bio-nano-
scholarship, he joined composites. He is
at University of Kassel, cross-appointed to the
Germany. He achieved Department of Chemical Engineering and Applied
his PhD in mechanical Chemistry. He is a fellow of Royal Society of
engineering at 2005. Chemistry, UK. Besides, he is also an adjunct professor
He worked at the of the Chemical Engineering Departments at the
Department of Forestry, Michigan State University, University of New Brunswick, Canada; King
USA as a visiting research associate from 2006 to Abdulaziz University, Jeddah, Saudi Arabia; Univer-
2009. Since 2010, he was working at the Centre sity of Guelph, Canada, University of Lulea, Sweden,
for Biocomposites and Biomaterials Processing, honorary professor at Slovak Technical University
University of Toronto, Canada. He joined Ford and Institute of Environmental Science at the Univer-
Motor Co. Canada as research and development sity of Toronto, and collaborates with American and
engineer on January, 2015. He has more than European research institutes and universities. Prof.
70 publications to his credits which have been Sain holds several awards; most recent one is the Plastic
published in different international journals and Innovation Award and Kalev Pugi Award for his inno-
conferences. He also edited one book, titled Biofiber vation and contribution to industry. Author of more
reinforcement in composites materials published than 300 papers, 6 books and hi-cited researcher Prof.
from Woodhead Publishing Ltd. In addition, he Sain hugely contributed to the society at large by
is invited reviewer of 58 international reputed translating research to commercialization which led
journals, government research proposals, and book to three new companies making products ranging
proposals. from packaging to automotive to building construction.

xv

Lignin is a complex polymer abundantly found in
plants and it is the fibrous part of the plant. Tradition-
ally, lignin is used in a wide range of low-volume,
niche applications. Industrial lignins are currently
obtained as coproducts of the manufacture of cellu-
lose pulp for paper, as well as from other biomass-
based industries and there are various types of lignin
depending on their process and purity. Lignin market
is still limited in its application in a wide range of low-
volume, niche applications, but lignin can be used in
a wide range of applications such as in the manufac-
ture of vanillin, animal feed, dye dispersants,
micronutrients, resins, and cleaning chemicals. In
addition, low awareness about lignin among manu-
facturers is the key restraint to this market. It is also
found that there is a weak link between the industry
and research institutes which results in the low
exposure of manufacturers to the developments of
lignin in different applications. Furthermore, the
extraction and modification techniques and applica-
tion of lignin are still at a primary stage, which
hampers the lignin market also. Another obstacle of
lignin expansion in value-added applications is
mainly due to their low-purity standards, heteroge-
neity, smell and color problems of the existing
commercial lignins.
Currently, environmental pollution and increasing
awareness of limited resources, there is growing
Preface
opportunity in the use of lignin as a substitute for
fossil-based raw materials and it could be used in
the manufacture of a wide range of products such
as plastics, chemical products, and carbon fibers.
Recently extensive ongoing research focusing on
lignin drawbacks is increasing the application scope
of lignin in the market.
In recent years, there have been a number of
review papers published on lignin covering lignin
chemistry, modification, polymer composites from
lignin, oxidative upgrade of lignin, biocomposites
and nanocomposites with lignin, industrial lignin
production and applications, and carbon fibers
from lignin. This book focuses specifically on
lignin-based polymer composites (thermoplastic,
thermoset, and biopolymer, rubber, nano, carbon),
lignin-based aerogels, lignin-based foaming mate-
rials, as well as sources and types of lignin, lignin
interunit linkages and model compounds, extraction
of lignin, characterization and properties of lignin,
and applications of lignin. The book will be helpful
to researchers, engineers, chemists, technologists,
and professionals who would like to know more
about the development and potential of lignin and
lignin-based composites.
Omar Faruk and Mohini Sain
xvii

Shayesteh Haghdan, Scott Renneckar and Gregory D. Smith
Department of Wood Science, Forest Sciences Centre, The University of British Columbia, Vancouver, BC, Canada
O U T L I N E
1. Introduction to Lignin
2. Lignin Functions
3. Sources of Lignin
3.1 Wood
3.2 Pulp and Paper Industry
1. Introduction to Lignin
The term lignin is derived from the latin name
lignum meaning wood (Mccarthy and Islam, 1999).
It was first isolated from wood in a scientific report
by the French scientist Payen (1838) and later given
its current name in 1857 by Schulze. Lignin was
initially described as an incrustant of cellulose, and
this point is insightful as lignification occurs after the
deposition of the polysaccharide framework. In an
extremely simplified view it is analogous to the
matrix material for a fiber-reinforced composite.
Lignin has several functions with the cell wall such as
changing the permeability and thermal stability, but it
has the primary function to serve as a structural
material that adds strength and rigidity to plant
tissue. In the sense lignin distinguishes lignocellu-
losic biomass from other polysaccharide-rich mate-
rials, by reinforcing the polysaccharide scaffolding of
the cell wall. Its performance is so effective that it
allows trees to outcompete other plants for sunlight
forming the largest organisms on the planet.
As lignin constitutes 15e40% of dry weight of
woody plants, it is the most abundant aromatic
polymer on the earth and the second most abundant
organic polymer after cellulose. Based on yearly
biomass growth rates, the overall production of
lignin is on the order of 5e36  108 tons (dos Santos
Lignin in Polymer Composites. http://dx.doi.org/10.1016/B978-0-323-35565-0.00001-1
Copyright © 2016 Elsevier Inc. All rights reserved.
1 Sources of Lignin
1 3.3 Sugarcane Bagasse 6
3.4 Agricultural Residues 7
4
4. Lignin Potential 8
5
5 References 8
6
et al., 2014). Hence, lignin has the potential to be an
important source of aromatic chemicals for the
chemical industry, arising from the conversion of
modern era CO2, and its efficient utilization solves
a potential puzzle in creating valuable by-products in
a biorefinery scheme. This reasoning is because if
wood is converted to the billion ton scale for biofuels
and biochemicals, then there will be greater than
300 million tons of lignin potentially available. To
put this in perspective it is roughly the size of the
global polymer market.
As mentioned above, lignin is an aromatic poly-
mer. The monomeric precursors have a phenolic ring
with a three carbon side chain providing a basic nine
carbon structure commonly referred to as a C9-unit
and/or phenylpropane unit as shown in Figure 1.
The side chain is terminated with a primary
hydroxyl group on the Cg, while the Ca and Cb are
connected together with an unsaturated bond. The
phenolic ring is methoxylated (eOCH3) to various
degrees, dependent upon the species; p-coumaryl
alcohol, coniferyl alcohol, and sinapyl alcohol have
none, one, or two methoxyl groups at the 3- and
5-positions, respectively. Based on the lignin mono-
meric composition involved in polymerization, the
resulting lignin is classified into three types: (1) lignin
that contains mainly coniferyl alcohol is called
guaiacyl (G) lignin and is found predominantely in
1
2 L IGNIN IN P OLYMER C OMPOSITES

Figure 1 Examples of C9 monomers: p-coumaryl alcohol, coniferyl alcohol, and syringyl alcohol.

gymnosperms; (2) lignin formed from sinapyl alcohol
is called syringyl lignin (S) and mixtures of G and S
are found in angiosperm lignin; and (3) lignin which
incorporates p-coumaryl alcohol is p-hydroxyphenyl
(H) lignin, and the three types of monomers are
commonly found in grasses. Overall hardwoods have
a G:S ratio that approaches 1:2 and softwoods have
approximately 95% G lignin (Lin and Dence, 1992).
One simple way of determining this ratio is based on
the methoxy content of the lignin, while other tech-
niques can be used to identify the specific C9 struc-
tures either directly using nuclear magnetic
spectroscopy or determined from the derivatized
thioacidolysis products using gas chromatography.
The monomeric units are built into the macro-
molecule lignin from the oxidative radical coupling
of these substructures (Adam et al., 2011; Dinis et al.,
2009; De la Cruz, 2014; Bowyer et al., 2007).
Lignification is initiated when a phenolic hydroxyl
hydrogen atom is abstracted by the enzyme peroxi-
dase to form a phenoxy free radical, typically
referred to as dehydrogenative polymerization, as
described by Freudenberg and Neish (1968). This
phenoxy-free radical will then delocalize to both
aromatic and side chain carbon atoms by the process
of resonance stabilization (Figure 2).
Coupling of these radicals may form ether link-
ages, carbonecarbon bonds, and bonds occasionally
to more than one other phenylpropane unit. Based on
the stability of the radical at each location, there is
a higher probability that certain carbons will host the
free radical. This, in turn, will provide preferred
linkages between lignin units. It has been determined
that approximately 50% of these bonds are b-O-4
ether type (De la Cruz, 2014; Bowyer et al., 2007)
with other bonds associated such as b-5, b-1, b-b,

Figure 2 Resonance stabilization of radicals that lead to interunit linkages in lignin.

1: S OURCES OF L IGNIN
Figure 3 Examples of interunit connections in lignin. Note, the diagram is to simply illustrate possible linkages
and this structure is not a representative “segment” of lignin.
and 5-5 (Figure 3). It is evident that the Cg retains its
hydroxyl group through this process, providing the
native lignin opportunity to also retain a certain level
of hydrophilicity. Furthermore, as indicated in
Figure 3, the benzylic carbon (at the Ca) is typically
highly unstable and undergoes reactions with nucle-
ophilic compounds. These reactions can lead to the
formation of a secondary hydroxyl group at the Ca by
reaction with water which is a reactive site for link-
ages to carbohydrates creating ligninecarbohydrate
complexes. These linkages formed to the poly-
saccharides are both ether and ester linkages
dependent upon the functional groups of the mono-
saccharide (Fengel and Wegener, 1983).
Analysis of lignin impacts several changes to its
native state making it difficult to have an exact
structure of lignin within the cell wall. However,
there are isolation methods that can be used to get
a better idea of the characteristics of a less severely
modified lignin. One such method involves the
resizing of wood into a fine flour through ball milling,
using cellulose-degrading enzymes to remove the
bulk of the polysaccharides and then an acidolysis
reaction to break several of the lignin carbohydrate
linkages (Wu and Argyropoulos, 2003). The isolation
of this enzymatic mild acidolysis lignin (EMAL)
preserves several aspects about lignin and is used as
a standard to compare other lignin isolation methods.
3
When analyzed using quantitative nuclear magnetic
resonance (NMR) spectroscopy, it reveals that the
quantity of functional groups is based on the quantity
of lignin (Granata and Argyropoulos, 1995). It is also
revealed that most lignins have w4 mmol aliphatic
hydroxyl groups attached to the side chain per gram
of lignin and 0.2e1 mmol free phenolic groups per
gram of lignin (Pu et al., 2011). Furthermore, it is
possible to analyze lignin within the whole cell wall
without the need for isolation. This approach requires
the milling of wood into a fine powder and then using
special solvents for cell wall dissolution. Dissolved
wood material is analyzed using two-dimensional
(2D) 13Ce1H heteronuclear single quantum coher-
ence NMR spectroscopy (Mansfield et al., 2012). The
technique can determine the relative concentrations
of interunit lignin structures providing an insight into
the structure of lignin.
As may be inferred from the above description of
isolating EMAL, there are two processes that occur
during delignification. The first involves breakage of
key ligninecarbohydrate linkages. This bond
breakage will allow extractability of the lignin as
seen during mild acidolysis of lignin where dilute
hydrochloric acid is used to break these linkages.
The second process involves cleavage of some of
the interunit bonds of lignin that may reduce
the molecular weight. Hence, delignification
4 L IGNIN
technologies dramatically impact lignin function-
ality and molecular weight. As a result, the proper-
ties of lignin related to its solubility are modified.
Several studies have shown that lignin can be frac-
tionated by using several solvents with largely
different solvent parameters (Moerck et al., 1986). A
small fraction of lignin may be soluble in a nonpolar
solvent like toluene, nonhydrogen bonding solvents
like dichloromethane, while other fractions are
soluble in more polar solvents like aliphatic alco-
hols. The different solubility of the fractions shed
light on the heterogeneous nature of lignin even if it
is isolated from a softwood lignin that contains 95%
guaiacyl lignin. Delignification can modify the
lignin to appreciative degrees by the addition of the
reactants such as sulfur or alcohol to the lignin or
increase the molecular weight (or change the inter-
unit linkages) by reactions of lignin with itself
during delignification. These isolation processes
result in lignin that contains acidic groups, lose
aliphatic hydroxyl groups, increase the free phenolic
groups by breakage of the b-O-4 linkage, and
contain more carbonecarbon bonds between units
(which are referred to as condensed structures).
Because of the variety of intermolecular linkages
between the precursors, lignin is also a highly
heterogeneous polymer (Fengel and Wegener, 1983;
Baucher et al., 1996). The variety of bonds results in
a branched lignin polymer with a potentially cross-
linked three-dimensional structure (Schmidl, 1992).
The recent literature has suggested that lignin may be
more uniform than previous thought, with either
linear chain topologies (Crestini et al., 2011) or even
being capped by specific lignin monomers (Sangha
et al., 2014). However, it is clear that lignin poly-
merization is left up to the fates of thermodynamics
as the polymerization process occurs outside the
control of the cell cytoplasm (Ralph et al., 2004).
Hence, the cellular control is limited to the produc-
tion and release of the monomers involved in ligni-
fication and the enzyme-activated dehydrogenated
monomers will polymerize with the growing lignin
chain.
Another important aspect of polymeric materials is
their molecular weight. Absolute knowledge about
lignin’s molecular weight has been difficult to ach-
ieve as removing lignin to analyze it automatically
impacts the lignin structure. Additionally, lignin
molecular weight measurements suffer from issues
surrounding solubility, aggregation, adsorption, and
fluorescence making it one of the most difficult
IN P OLYMER C OMPOSITES
polymers to analyze. Early experiments looking into
the molecular weight of lignosulfonates suggested
that delignification occurred like breaking a network
polymer (Gorning, 1971). However, several different
isolated lignins have been analyzed with modern
analytical equipment, and lignin usually has
a bimodal distribution with number-average molec-
ular weight between 3000 and 10,000 and weight-
average molecular weight from 8000 to 80,000
dependent upon solution conditions, and lignin type
(Guerra et al., 2007). Many technical lignins
described in the literature either have lower molec-
ular weights because of fragmentation of lignin into
oligomers or much greater molecular weights. When
delignification occurs, a number of reactions can
occur but many involve radical formation and
subsequent radical coupling where lignin fragments
can become bonded, increasing the molecular weight.
Additional heterogeneity of lignin involves how
the structure of this polymer differs within a given
cell wall dependent on its location in the wall, plant
species (hardwood vs softwood), and growth
conditions, especially related to reaction wood
formation (Campbell and Sederoff, 1996; de Wild
et al., 2010). These differences arise from the
monomeric composition available during the ligni-
fication reactions. Overall, one can see the
complexity of trying to analyze a lignin that may be
different in various locations of the cell wall. Ter-
ashima has shown that lignin microstructure is
dependent upon its location in the cell wall. In the
cell wall corners, lignin forms spherical clusters,
while lignin in the secondary cell wall is greatly
reduced in dimensions surrounding the microfibril
lamellar structure of the cell wall layers as shown in
Figure 4 (Terashima et al., 2004). Work with the
Raman spectroscopy has indicated that lignin in
the secondary wall has a preferred orientation along
the microfibril structure (Atalla and Agarwal, 1985).
2. Lignin Functions
Lignin is part of the structural framework in
plants, forming part of the primary load-bearing
element of the cell wall. From an evolutionary
point of view, lignin has been credited as the terres-
trial adaption that permits significant vertical growth.
As an essential part of the cell, lignin supports the
plant by imparting rigidity to the cell wall. The plant
withstands natural environmental stresses because of
1: S OURCES OF L IGNIN
Figure 4 Cell corner region. Large globular modulus form aggregates at random, left and lignin modules (arrows)
are growing along cellulose microfibrils (CMFs) at an almost regular distance, right.
this cell wall building block (Lopes et al., 2011;
Sarkanen and Ludwig, 1971). Lignin not only
provides stiffness to the plant but in conjunction with
the heteropolysaccharides, it provides flexibility
which is fundamental for an appropriate response to
dynamic loads from wind and snow. In addition to
mechanical support, lignin modifies the poly-
saccharide network to make it resistant to outside
organisms. Lignin helps to protect woody tissue from
the microbial and fungal attack encasing the carbo-
hydrate structure, providing reduced accessibility of
enzymes for hydrolysis. Limited solubility and
complexity of the lignin make it resistant to degra-
dation by most microorganisms (Prasongsuk et al.,
2009; Bholay et al., 2012; Berg and Meentemeyer,
2002; Crow et al., 2009; Verma and Dwivedi, 2014).
One can imagine if lignin only contains a single
linkage that would become the cell wall’s Achilles’
Heal. However, with the variety of linkages wood-
destroying organisms require the breakage of both
aryl carbon bonds and aryl ether bonds needing to
expand the cost of production of specific enzymes or
develop nonspecific pathways for delignification. In
addition, lignin is less hydrophilic than the poly-
saccharides helping to change the permeability of the
cell wall by sealing it and enabling water transport
through the vascular tissue (Ten and Vermerris,
2013). Finally, the aromaticity of lignin lends itself to
enhance the thermal stability of wood providing char
layer. This has been exploited with isolated technical
lignin, turning it into carbon fiber material by
controlled high-temperature heating. While lignin is
seen as more thermally stable because of it, the native
structure of lignin is greatly impacted by the thermal
modification and researchers should be cautioned
5
that lignin structure can change during processing at
temperatures used in the production or some ther-
moplastic materials. Such modification includes
depolymerization, loss of the Cg hydroxyl, and
formation of new acidic groups.
3. Sources of Lignin
The source from which lignin is obtained, the
extraction methods and the secondary treatments
applied, have strong impacts on its physical and
mechanical properties (Garcia et al., 2011; Khanam
et al., 2006). Lignin can be derived from various
sources such as wood, pulp and paper, sugarcane
bagasse, and cereal straws using a variety of pulping
methods. In terms of weight, the lignin content in
woody plants from gymnosperms and angiosperms is
the highest with the order of 30e40% while other
sources only contain around 3e25% (Smolarski,
2012). The pulp and paper sector produces a large
amount of lignin (Jungmeier, 2010; Doherty et al.,
2011) with even greater potential from future ligno-
cellulosic biorefineries. Minimal lignin is recovered
from grass, branches, leaves, and solid waste in urban
and rural areas where their lignin content is estimated
to be less than 15% (Wang et al., 2011; Philippidis
and Hatzis, 1997).
3.1 Wood
Lignin has nonuniform thickness in the middle
lamella, and in the primary and secondary cell walls
depending on the plant species and cell type
(Figure 5). Approximately 70% of the total lignin
content of the cell wall is concentrated in the
6 L IGNIN
thickest layer of the secondary cell wall. Lignin
quantity and quality vary naturally among wood
species with 19e28% in hardwoods (angiosperms)
and 24e33% in softwoods (gymnosperms) (Fengel
and Wegener, 1983). In fact, hardwoods, in general,
contain more hemicellulose and less lignin than
softwoods (Bjornsson, 2014). Not only the amount
of lignin varies between hardwoods and softwoods,
the relative concentration also differs in the location
within a tree. The juvenile wood has a higher lignin
content than latewood (De la Cruz, 2014; Bowyer
et al., 2007). Lignin content is also variable within
populations of plants of the same genus. For
example, the average content of lignin ranges from
25% in Pinus monticola to 30% in Pinus palustris
within the genus Pinus. Reaction wood forms
mechanical stress and has different lignin content in
comparison with the normal wood depending on the
conditions and species (Tiimonen, 2007).
Lignin in hardwoods is syringyleguaiacyl type
and in softwoods is typically guaiacyl with limited
p-hydroxyphenyl lignin in both types. Both of these
structures have differences arising from the interunit
linkages. Guaiacyl lignin can undergo coupling
reactions at the 5-position of the phenylpropane unit,
and this provides a significant place for branching and
cross-linking reactions, especially occurring during
Figure 5 Wood cell wall including middle lamella (ML),
primary cell wall (P), layers of the secondary cell wall
(S1, S2, S3), and warty layer (W) (Sjostrom, 1993).
IN P OLYMER C OMPOSITES
delignification process. The presence of syringyl units
makes hardwood lignin more readily removed during
the pulping process by limiting lignin forming
condensed structures at the open methoxy position. In
the case of compression-wood lignin, it is more
difficult to hydrolyze because it contains a higher
proportion of condensed p-hydroxyphenyl units
(Campbell and Sederoff, 1996; Novaes et al., 2010).
3.2 Pulp and Paper Industry
Softwood and hardwood species, and certain types
of annual plants, have commercial interest as a source
of cellulose fibers for the production of paper and
board products. Lignin is not easy to isolate in the
native form from plant material (Leisola et al., 2012).
The pulp and paper industry is the primarily
commercial source of lignin, however, the delignifi-
cation process modifies lignin to various degrees. In
technical fiber liberation processes, such as alkaline
or sulfite pulping, huge quantities of lignin are dis-
solved as alkali lignin and lignosulfonates, respec-
tively. Large amounts of lignin are made available
annually from the pulp and paper industry as by-
products of the delignification process. These sulfite
or sulfate lignins have varying levels of covalently
bonded sulfur resulting in the polymer with different
characteristics than the original lignin (Sainsbury,
2013; Khanam et al., 2006; Lora and Glasser, 2002).
Typically, lignin impurities include low-molecular-
weight sugars and resin acids that are removed during
the purification process. For example, kraft lignin is
usually purified from kraft black liquors which are
complex mixtures of fibrous materials and dissolved
organics such as lignins, hemicelluloses, sugars, acids,
and resins and also inorganic salts such as ash (Wall-
berg et al., 2003). The recent technology in enhancing
lignin recovery from black liquor by CO2 acidification
has been transferred to the industry and has created
a readily available dry lignin powder stream (Ohman
et al., 2013; Kouisni et al., 2012). As shown in Table 1,
in all commercial pulping processes the lignin
extraction methods will affect the value of the products
that can be derived from it and will alter the structure of
the lignin in comparison with the native one (Smo-
larski, 2012).
3.3 Sugarcane Bagasse
Sugarcane bagasse is the fiber that remains after the
sugars have been extracted. As an agro-industrial
residue, sugarcane bagasse (Saccharum officinarum)
1: S OURCES OF L IGNIN
Table 1 Lignin Purity with Its Associated Sources (Holladay et al., 2007)
Lignin Type Lignin Puritya
Lignosulfonates Medium (some reducing sugar
(up to 20 wt%) and sulfur)
Kraft Medium (some ash and sulfur)
Organosolv High (sulfur free)
a
Presence of residual carbohydrates, ash, and proteins depends on feedstock and process.
is another source of lignin raw material. It is a by-
product of the sugarcane industry with approxi-
mately 32e34% cellulose, 19e24% hemicellulose,
25e32% lignin, 6e12% extractives, and 2e6% ash
(Sakdaronnarong and Jonglertjunya, 2012; Rezende
et al., 2011; Pandey et al., 2000). Chemical compo-
sition of sugarcane bagasse is similar to the other plant
cell walls. Each class of plants, grasses, softwoods,
and hardwoods produces a lignin rich in one type of
the phenylpropane repeat unit. Sugarcane bagasse
lignin has a higher proportion of H-type lignin, p-
hydroxyphenyl, and hence a lower methoxy content
than softwood and hardwood lignins (Doherty et al.,
2007). Approximately 250e280 kg of bagasse is
generated from processing each ton of sugarcane
which roughly yielded 54 million tons of bagasse
annually (Canilha et al., 2012). Currently, a large
amount of bagasse is burnt as a low-grade fuel for
energy recovery, and only a limited quantity has been
used to make pulps, board materials, and composites.
It is estimated that 200 million tons of lignin is
produced annually from bagasse (Singh et al., 2005).
3.4 Agricultural Residues
The advantages of using agricultural residues are
threefolds: economic, environmental, and techno-
logical. Unlike wood pulps, agricultural pulps can be
produced using more environmentally benign pro-
cessing and bleaching methods (Clancy-Hepturn,
1998). In the wood pulping process, most of the pulp
is bleached using chlorine or chlorine-based chem-
icals while straw can be treated with minimal addi-
tions of chlorine-free chemicals which results in no
production of toxic chemicals. Moreover, agricul-
tural residues have generally a more porous structure
and a lower lignin content than woody plants which
facilitate their pulping process. Examples of the
7
Potential Products
Dispersants, agricultural chemicals, emulsion
stabilizer, industrial binders, carbon black, ink
and pigments, and concrete additives
Dispersants, carbon fibers, emulsifiers,
activated charcoal, and binders
Aromatic polyols, new diacids, activated carbon,
phenolic resins, carbon fibers, vanillin, phenol
derivatives, and antioxidants
agricultural residues are rice and wheat straws which
are discussed in this section. Rice straw also called as
cereal straw is another source for lignin production.
Total world production of rice straw, Oryza sativa, is
525 million tons per year.
About 90% of the rice straw is produced in Asia.
China has the greatest capacity for pulping rice straw.
It has approximately 30e35% cellulose, 25e30%
hemicellulose, 15e28% lignin, and 4e7% ash
(Marques et al., 2010). The high ash content arises
from the silica in the cell wall limiting the ability to
burn this material without causing a significant envi-
ronmental nuisance. High silica content in rice straw,
as high as 18% in clean rice straw, makes the pulping
process more costly due to increased chemical
recovery difficulties and costs. In addition to rice
straw, wheat straw, Triticum aestivum, is annually
generated in abundance of 529 million tons per year.
When farmed intensively, wheat straw can be
produced in a larger scale. The amount of lignin of
wheat straw varies between 5% and 17% depending
on the geographical location of the plants which is
comparable to hardwoods (Buranov and Mazza,
2008). Wheat straw has one of the highest cellulose
contents of all of the agricultural fibers. Straw papers
are known to possess good printing qualities and are
made from pulp requiring low energy relative to that
required to process wood pulp. Researchers found that
wheat straw must be pulped under conditions of less
energy and fewer chemicals in comparison with the
wood pulps to maximize pulp yields (Clancy-Hepturn,
1998). To make the strongest product, papermakers
will likely combine some stronger hardwood, kenaf,
or hemp pulp with straw pulp. Despite the advantages
of using agricultural residues, the high collection,
transportation, and handling costs associated with
these resources, as well as their seasonal availability,
limit their applications in paper production.
8 L IGNIN
4. Lignin Potential
Currently around 50 million tons of lignin is
produced per year by the pulp and paper sector but only
2% of that is used for applications other than combus-
tion and energy production (de Wild et al., 2014; Fengel
and Wegener, 1983; Schmidl, 1992; Thielemans et al.,
2002). There are limitations in utilization due to the
lignin structure, heterogeneity, and the industrial pro-
cessing costs for delignification (Holladay et al., 2007;
Vanholme et al., 2010; Neutelings, 2011; El Hage et al.,
2009; Chiang, 2005). To improve upon these limita-
tions, different types of modifications are done to
increase its chemical reactivity and uniformity, reduce
the brittleness of lignin-derived polymers, increase its
solubility in organic solvents, and improve the ease of
processing the lignin (Argyropoulos, 2012). Lignin
potentials can also be considered in the production of
additives, resins, and coating materials (Jungmeier,
2010; Vishtal and Kraslawski, 2011). This renewable
aromatic polymer can equally be replaced with
synthetic polymers and aromatic chemicals (Zakzeski
et al., 2012). High antioxidant capacity of lignin and its
applications in polymer enhancement have been
experimentally proved (Piazza et al., 2014). The find-
ings of research on lignin depolymerization showed
that due to the ligninmacromolecular structure of lignin
with many phenolic units, lignin depolymerization can
be used as a large-scale source for production of valu-
able chemicals (Kleinert et al., 2009; Meier et al., 1992;
Horácek et al., 2012). Lignin also has potential to be
used in the fabrication of composite materials.
El Mansouri et al. (2007) showed that exterior-grade
particleboards made with lignin-based adhesives
successfully met the requirements of international
standards. The potential of lignin in polymeric
composites will be discussed in later chapters.
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9164(03)80019-X.
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15567030903226249.
de Wild, P.J., Huijgen, W.J.J., Gosselink, R.A., 2014.
Lignin pyrolysis for profitable lignocellulosic bio-
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de Wild, P.J., van der Laan, R.R., Wilberink, R., 2010.
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Wu, S., Argyropoulos, D.S., 2003. An improved
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Zakzeski, J., Jongerius, A.L., Bruijnincx, P.C.A.,
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http://dx.doi.org/10.1002/cssc.201100699.
 2 Extraction and Types of Lignin
Hoyong Chung 1 and Newell R. Washburn 2,3
1
Department of Chemical and Biomedical Engineering, Florida State University,
FAMU-FSU College of Engineering, Tallahassee, FL, USA
2
Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, USA
3
Department of Biomedical Engineering, Carnegie Mellon University, Pittsburgh, PA, USA

O U T L I N E

1. Introduction 13 2.5 Steam Explosion Lignin (Hydrothermal

Process) 20
2. Commercial-Grade Lignins 15
2.6 Dilute Acid Lignin 21
2.1 Kraft Pulping 16
2.2 Sulfite Pulping 16 3. Conclusions 22
2.3 Soda Process 18
References 22
2.4 Organosolv Lignin 19

1. Introduction comprising primarily of G-units with small concen-

Lignin is the second most abundant terrestrial
biopolymer after cellulose and is the largest renew-
able source of aromatic groups in nature. Lignin is
found in plant cell walls and is an important struc-
tural component of woody plants. The main functions
of lignin in plants are to provide physical strength,
to form water-conducting vascular networks using
hydrophobic interactions and to protect plants from
microorganisms and insects. Chemically, lignin is
composed of a random network of phenylpropane
groups. The three basic structural monomer units are
coumaryl alcohol, coniferyl alcohol, and sinapyl
alcohol, as shown in Figure 1. In nature, these
monomer units oxidize to phenoxy radicals by
peroxidase and then undergo polymerization through
multiple reactive sites to form a complex three-
dimensional polymer. This biosynthesis is referred
to as dehydration polymerization, and the resulting
monomer units within lignin are referred to as
p-hydroxyphenyl (H), guaiacyl (G), and syringyl
(S). Differences in lignin according to various plant
sources can be manifested in differences in mono-
mer concentrations (Vanholme et al., 2010), with
gymnosperms, such as the various types of pines,
trations of H-units. In contrast, angiosperm dicots,
including many hardwoods, have a mixture of G and
S-units, which reduce branching concentrations and
can improve lignin processibility.
As a result of the random radical polymerization of
phenylpropane monomers, lignin adopts complex
three-dimensional structures with various types of
functionality. As shown in Figure 2, important CeO
linkages are b-O-4, a-O-4, and 4-O-5; and CeC links
are b-5, 5-5, b-1, and beb linkages (Koch, 2008;
Calvo-Flores and Dobado, 2010). Also, common
functional groups in lignin include methoxyl, phenolic
hydroxyl, aliphatic hydroxyl, and other carbonyl
groups (Chakar and Ragauskas, 2004).
Figure 1 Monomeric lignin building blocks: p-coumaryl
alcohol, coniferyl alcohol, and sinapyl alcohol.

Lignin in Polymer Composites. http://dx.doi.org/10.1016/B978-0-323-35565-0.00002-3

Copyright © 2016 Elsevier Inc. All rights reserved. 13
14
Figure 2 Schematic model of the lignin structure with important linkages (Koch, 2008; Calvo-Flores and Dobado,
2010; Laurichesse and Averous, 2014).
Chemical characterization of lignin, lignin deriv-
atives, and other lignin-based materials is not a
simple task due to the three-dimensional architecture,
diversity of chemical linkages and functional groups,
difficult isolation, and poor solubility in many
organic solvents (Figure 2). This is further compli-
cated by many different types of lignin depending on
the plant source and processing method. Numerous
analytical approaches have been employed to char-
acterize the structure of lignin and other lignin-based
materials.
Nuclear magnetic resonance spectroscopy is one of
the most useful techniques to determine the chemical
structure of lignin (Ralph et al., 1999; Ralph and
Landucci, 2010). Lignin contains a high fraction of
methoxy groups and aromatic hydrogens, allowing
these groups to be readily determined by 1H NMR.
However, 1H NMR is not suitable for characterizing
the most abundant reactive group, the hydroxyl group.
Hydroxyl group content is best determined after
acetylation of hydroxyl groups by acetic anhydride
in the presence of pyridine (Bonner and Mcnamara,
1968; Chung and Washburn, 2012). The acetoxy
groups produced in this reaction correspond to
L IGNIN IN P OLYMER C OMPOSITES
hydroxyl groups of lignin and appear at chemical
shifts of approximately 2 ppm (Lundquist, 1992;
Chung and Washburn, 2012). After acetylation, the
phenolic hydroxyl group can be determined selec-
tively by relatively fast and selective deacetylation
of phenolic acetyl groups (Månsson, 1983). Alkyl-
ation of the hydroxyl group was performed to deter-
mine hydroxyl groups in 1H NMR spectra (Adler
et al., 1987). While 1H NMR provides quantitative
information, certain peaks, such as those due to
methoxy groups, can appear broad and featureless
because of the diversity of chemical environments
(Liitia et al., 2003). Two-dimensional 1H-13C NMR
spectroscopy can provide detailed information on
connectivity. Model lignin complexes provided
detailed information necessary for peak assignments
(Ede and Ralph, 1996), and numerous pulse sequences
have been developed to elucidate the connectivity of
functional groups and identify specific linkages
(Ede and Brunow, 1992; Kilpelainen et al., 1994).
For example, the syringyl-to-guaiacyl (S/G) ratio
was followed during kraft pulping using hetero-
nuclear single quantum correlation NMR, which
provided information on changes due to oxidation
2: E XTRACTION AND T YPES OF L IGNIN 15

during processing (Ibarra et al., 2007). A different
approach that provides information on alcohol
functionality utilizes 31P NMR in which hydroxyl
groups were converted to phosphityl groups by
2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane
to do 31P NMR analysis (Granata and Argyropoulos,
1995; Froass et al., 1998). For 31P NMR analysis,
phosphitylation was carried out by another agent,
1,3,2-dioxaphospholanyl chloride (Argyropoulos,
1994; Froass et al., 1996). Most of the lignins from
the processing methods described here have been
characterized by NMR spectroscopy.
Size-exclusion chromatography (SEC) analysis of
lignin is an important analysis to determine molecular
weight and molecular weight distribution, which are
critical data for materials development (Himmel et al.,
1995; Hortling et al., 1995). However, the reliability
of SEC analysis can be limited due to the many
functional groups in lignin, such as hydroxyl groups
and carboxylic acids, and the lignin analyte can have
strong interactions with the column support materials
or between other lignin species (Sarkanen et al., 1981,
1982, 1984; Iversen, 1985). Therefore, the hydroxyl
groups are acetylated and carboxylic acid groups
are methylated prior to the SEC analysis to exclude
possible noncovalent interactions, such as hydrogen
bonding and electrostatic aggregation, from the lignin
(Himmel et al., 1995; Kim et al., 2007). Lignin is also
characterized by various morphological methods such
as thermal analysis and Raman/IR analysis (Agarwal
and Atalla, 1999, 2010; Glasser Wolfgang, 1999).
The chemistry and material properties of lignin
have been reviewed extensively (Goldstein et al.,
1983; Lewis et al., 1999; Chakar and Ragauskas,
2004; Calvo-Flores and Dobado, 2010; Hatakeyama
and Hatakeyama, 2010; Duval and Lawoko, 2014) as
well as chemical methods for modifying and blending
it (Wang et al., 1992; Meister, 2002; Liitia et al.,
2003; Mohanty et al., 2009; Doherty et al., 2011;
Washburn and Chung, 2012). In this chapter, we
present extraction methods and types of commercial-
grade lignin from a raw biomass. A better under-
standing of types and production methods of lignin is
an important starting point to study lignin as new
materials, biofuel, and renewable sources of fine
aromatic chemicals.
2. Commercial-Grade Lignins
Lignin is biosynthesized from monomeric substi-
tute phenyl propylene units, coumaryl alcohol, con-
iferyl alcohol, and sinapyl alcohol, as lignocelluloses
as well as nonconjugated lignin. Because the ligno-
celluloses and lignin are intimately incorporated in
plant structures, a variety of processing methods have
been developed to isolate lignin. Table 1 demon-
strates diverse sources of lignin from raw biomass

Table 1 Polymeric Components of Raw Biomass and Plant-based Materials (Suchy and Argyropoulos, 2002;
Koch, 2008)

Source (%) Lignin Hemicellulose Cellulose Extract

Hardwood 16e24 25e35 43e47 2e8
Softwood 25e31 25e29 40e44 1e5
Bagasse 20 30 40 10
Coir 43e49 10e20 32e43 4
Corn cobs 15 35 45 5
Corn stalks 35 25 35 5
Cotton 1 2 95 0.4
Flax (retted) 2 21 71 6
Flax (unretted) 3 12 63 13
Hemp 6 22 70 2
Jute 13 14 71 2
Sisal 11 14 73 2
Wheat straw 15 50 30 5
16
and plant-based materials such as cotton and
bagasse. Raw wood species, hardwood, and soft-
wood contain a high percentage of lignin, between
25% and 40%. Lignin and other polymeric compo-
nents of each wood species differ as shown in
Table 2. Glucomannan and glucuronoxylan are typical
types of hemicellulose in each woody species. Over
the all woody species, the portion of the lignin is at
least 20%. Therefore, it is necessary to isolate two
important plant-based polymers, lignin and cellulose,
from raw biomass resources through an efficient,
industrial-scale method. Each commercial isolation
method has trade-offs in terms of reagents and energy
required that affect the molecular weight and purity
of the final product, as well as the extent to which
new chemical functionality is introduced as a result
of processing. The pulp and paper industry is the
major producer of commercial-grade lignin as a by-
product of cellulose-rich pulp/paper manufacturing
but cellulosic ethanol facilities are currently coming
online. It is critical for researchers to understand how
lignin processing has changed the chemistry and
properties of the material. Six common commercial-
grade lignin-producing methods are discussed here.
2.1 Kraft Pulping
The kraft pulping process is the most commonly
used chemical pulping methods to produce cellulose
fibers from raw wood and plant sources (Sixta et al.,
2008). The global production using kraft pulping is
the largest among all production methods with
131.2 M ton in 2000 (Sixta et al., 2008), making kraft
lignin the most common form (Smook, 2002). Kraft
pulping is a method of chemical pulping that uses
chemical reactions to degrade and dissolve the lignin
in order to separate pure cellulose from the wood
(Sixta et al., 2008). An important step of kraft pulping
is a treatment of biomass with sodium hydroxide and
sodium sulfide to cleave ether linkage by sulfide and
bisulfide ions (Sjöström, 1993). In this process,
phenolic groups are converted to quiononemethide
groups by sodium hydroxide and then hydrogen
sulfide ion attacks a-carbon atoms of ether linkages
forming a benzylthiolate anion. Next, the b-phenolate
anion is released from the benzylthiolate anion to
produce free phenolic groups. The free phenolic
groups yield quiononemethide again, and the same
process is repeated to cleave ether bonds continuously
and produce lower molecular weight, soluble frag-
ments. Lignin carbonecarbon bonds can be formed at
L IGNIN IN P OLYMER C OMPOSITES
the last stage of the process; this generally involves
a condensation reaction and yields a very robust
lignin complex (Saake and Lehnen, 2000; Sixta et al.,
2008) (Schemes 1 and 2). Kraft lignin is hydrophobic
at neutral pH and contains approximately 1% sulfur
(measured in atomic%) in the form of aliphatic thiol
groups (El Mansouri and Salvado, 2007). Also other
important functional groups in kraft lignin (expressed
in w/w%) are methoxy group (14%), aliphatic
hydroxyl group (10%), phenolic hydroxyl group
(2e5%), and carboxylic acid group with composi-
tions that can vary depending on the plant source and
processing conditions (4e7%) (El Mansouri and
Salvado, 2007; Doherty et al., 2011). However, as
a by-product in paper production, most kraft lignin is
still burned as a fuel to produce power in the pulp mill
and to recover inorganic components (Saake and
Lehnen, 2000; Mohanty et al., 2009; Doherty et al.,
2011).
2.2 Sulfite Pulping
The process of sulfite pulping is the reaction of
wood or biomass with sulfur dioxide (SO2), which
reacts with water to form sulfonic acid, and bases such
as calcium, sodium, magnesium, or ammonium at
high temperatures, 125e150
C, for 3e7 h. This
process is acid-catalyzed to cleave a-ether linkage
and b-ether linkages during the pulping process
(Shimizu et al., 1998). The lignin can be dissolved and
separated in aqueous solution due to sulfonic acids
which introduced to a-carbon of ether linkage (Saake
and Lehnen, 2000). The resulting lignin has func-
tional groups of lignosulfonic acid, lignosulfonate,
carboxylic group together with phenolic/aliphatic
hydroxyl groups (Vishtal et al., 2011). Due to the high
content of sulfonate, the produced lignin is water
soluble. Lignin produced by the sulfite process has
broad molecular weight distribution and relatively
high ash content. The carboxylic acid content is
approximately 4%, while the sulfonate content can be
13% (El Mansouri and Salvado, 2007). Thus, the
materials applications are limited to the area of
animal feeds, particle boards, surfactants, adhesives,
cement additives, and stabilizer/dispersing agents
(Vishtal et al., 2011; Laurichesse and Averous, 2014).
Due to the high content of sulfur, approximately
5e6%, most of the obtained lignin by the sulfite
pulping process is used as a fuel for the pulp mill and
to recover inorganic components (Saake and Lehnen,
2000; Doherty et al., 2011) (Scheme 3).
Table 2 Polymeric Components of Various Softwood and Hardwood Species (Sjöström, 1993; Koch, 2008)

Species Common Names Extractives Lignin Cellulose Glucomannan Glucuronoxylan Polysaccharides

Softwoods
Abies balsamea Balsam fir 2.7 29.1 38.8 17.4 8.4 2.7
Pseudotsuga Douglas fir 5.3 29.3 38.8 17.5 5.4 3.4
menziesii
Tsuga Eastern hemlock 3.4 30.5 37.7 18.5 6.5 2.9
canadensis
Juniperus Common juniper 3.2 32.1 33.0 16.4 10.7 3.2
communis
Pinus radiate Monterey pine 1.8 27.2 37.4 20.4 8.5 4.3
Pinus sylvestris Scots pine 3.5 27.7 40.0 16.0 8.9 3.6
Picea abies Norway spruce 1.7 27.4 41.7 16.3 8.6 3.4
Picea glauca White spruce 2.1 27.5 39.5 17.2 10.4 3.0
Larix sibirica Siberian larch 1.8 26.8 41.4 14.1 6.8 8.7
Hardwoods
Acer rubrum Red maple 3.2 25.4 42.0 3.1 22.1 3.7
Acer saccharum Sugar maple 2.5 25.2 40.7 3.7 23.6 3.5
Fagus sylvatica Common beech 1.2 24.8 39.4 1.3 27.8 4.2
Betula verrucosa Silver birch 3.2 22.0 41.0 2.3 27.5 2.6
Betula papyrifera Paper birch 2.6 21.4 39.4 1.4 29.7 3.4
Alnus incana Gray alder 4.6 24.8 38.3 2.8 25.8 2.3
Eucalyptus Blue gum 1.3 21.9 51.3 1.4 19.9 3.9
globulus
Acacia mollissima Black wattle 1.8 20.8 42.9 2.6 28.2 2.8
18 L IGNIN IN P OLYMER C OMPOSITES

Scheme 1 Reaction of b-aryl ether linkages in nonphenolic phenylpropane units.

Scheme 2 Reaction of sulfide with phenolic phenylpropane units. Styrenic products are capable of further reac-
tions to form a complex polymer mixture.

Scheme 3 Mechanism of lignin isolation during the sulfite pulping process.

2.3 Soda Process As shown in Scheme 4, an a-ether bond can be

The soda process is the oldest pulping method
that uses sodium hydroxides as the chemical
reagents of the pulping process, and is now being
used to process nonwood material, which includes
mainly annual plants and agricultural waste, such as
wheat straw, sisal, kenaf, hemp, and bagasse. In this
process, biomass reacts with concentrated sodium
hydroxide (ca. 1 M) under high temperature (ca.
170
C) and high pressure (ca. 10 psi) (Gierer, 1980).
hydrolytically cleaved by this method, resulting in
lower molecular weight fragments with increased
solubility, making it an effective process for
delignification.
Anthraquinone (AQ) is often added to the reaction,
which oxidizes carbohydrates and forms anthrahy-
droquinine (AHQ) (Lundquist et al., 1981). The AHQ
dianion can cleave the b-O-4 ether linkage easily
during the process by reacting with quinine methides
formed from soda reactions via nucleophilic attack,
2: E XTRACTION AND T YPES OF L IGNIN
Scheme 4 Cleavage of the a-ether bond in lignin
during the soda process.
thus regenerating the AQ. This reaction is shown in
Scheme 5.
Addition of AQ can significantly increase the
delignification rates; Lunquist et al. reported a
reduction in cooking time from 250 min for soda to
90 min for soda-anthraquinone in studies on spruce
wood (Lundquist et al., 1981). Furthermore, soda
lignin has been used as a precursor for raw materials
that is considered as being closer to natural lignins in
a broad range of applications because of the absence
of sulfur functionality (Gierer et al., 1979; Saake and
Lehnen, 2000).
2.4 Organosolv Lignin
Organosolv processes represent a large family of
methods used to delignify biomass, and there are
several excellent reviews on these (McDonough,
1993; Young and Akhtar, 1998). Common features
include mixtures of water and organic solvents to
remove lignin from the wood or other biomass as well
as the use of acid or base catalysts (Pye and Lora,
1991; Stockburger, 1993; Akhtar and Young, 1997;
Zhang et al., 2007). Ethanol, methanol, formic acid,
or acetic acid have been used, and it is known that the
organosolv process is more effective in treating
annual plants and hardwoods (Pye and Lora, 1991;
Lora et al., 1993; Creamer et al., 1997). Organosolv
lignin is free of sulfur, and the molecular weight is
low compared to other lignin production methods,
generally around 5 kDa, although this will depend on
the organic solvent used, with carboxylic acids often
Scheme 5 Cleavage of the b-O-4 ether linkage in the presence of anthrahydroquinine in the soda process.
19
being less effective at preventing recombination
than alcohols. However, the use of organic solvents
increases the cost of processing and can have a
greater environmental impact, although the lack
of odor of this process compared to the kraft process
and its compatibility with agricultural residues
provide some benefits in this regard (Pye and Lora,
1991; Stockburger, 1993; Akhtar and Young, 1997;
Zhang et al., 2007). Many organosolv processes
have been investigated extensively and tested in pilot-
scale plants, including Alcell, Acetosolv, and Milox.
Most involve an acid catalyst or are performed in an
acidic solvent, which allows use of lower tempera-
tures than traditional pulping methods, and they
generally avoid use of sulfur- and chlorine-based
chemicals.
The Alcell method is based on ethanol processing
using a sulfuric acid catalyst, which is being actively
studied for the pretreatment of lignocellulosics for
ethanol production. Ethanol more efficiently solubi-
lizes lignin cleavage products formed as a result of
catalyst action than water. While originally devel-
oped for hardwoods, recent studies have focused on
adapting this for softwoods, such as pine (Pan et al.,
2005), as well as agricultural residues (Cybulska
et al., 2012). Optimized conditions for softwood
were found to be 170
C, 60 min, 1.1% H2SO4, and
65% ethanol/35% water from which 79% of the
lignin was recovered (Pan et al., 2007). As deter-
mined using 13C and 31P NMR measurements, the
major reaction products from processing pine were
formed through cleavage of the b-O-4 linkages as
well as ester bonds (Sannigrahi et al., 2010). Char-
acteristic molecular weights for these lignins are
Mw w2000 g mole1 with a polydispersity of w2.0.
Interestingly, ethanol organosolv products tend to be
richer in phenolic hydroxyl groups, making them
highly effective at radical scavenging (Pan et al.,
2006).
The Acetosolv process uses a cooking medium
of 93% acetic acid and <1% hydrochloric acid as
a catalyst. The addition of a mineral acid catalyst allows
20
for lower digestion temperatures, often below 140
C
instead of 170
C or greater without it. The kinetics of
the Acetosolv process have been studied for both hard-
wood (eucalyptus) and softwood (pine) (Vazquez et al.,
1997). The proposed mechanism is based on a sequence
of first-order reactions involving formation of soluble
lignin species through lignin hydrolysis, lignin conden-
sation in solution, and subsequent reprecipitation.
Effective delignification was observed at 180
C and
0.1% HCl, whereas increasing the HCl concentration to
0.2% allowed for a temperature reduction to 140
C, but
longer reaction times can actually reduce yield due to
lignin recombination.
The Milox (or Formacell) process takes its name
from the Milieu Pure Oxidative process developed
by the Finnish Pulp and Paper Research Institute
(KCL) (Sundquist, 1986). It is based on use of per-
oxyformic acid to perform tandem delignification
and bleaching. Peroxyacids react with nucleophiles
having p-electrons via oxygen transfer, and in
acidic media the strong electrophile þOH is formed.
A diversity of functional groups result from this
oxidation reaction, including quinones, carboxylic
acids, and alkenes, and formation of recombination
by-products is minimized through efficient solubili-
zation in the water/formic acid medium.
Generation of peroxyformic acid is accomplished
by reacting formic acid with hydrogen peroxide
according to the reaction:
which has a forward rate constant at 22
C that is 50
times greater than the analogous reaction of acetic acid
and hydrogen peroxide (Suchy and Argyropoulos,
2002). Peroxyformic acid can be readily separated
from the reaction mixture by distillation, and has been
applied to the reactor as a concentrated solution.
However, these concentrated solutions can be explo-
sive, and more recent approaches rely on generating it
in situ. Seisto et al. (Seisto and PoppiusLevlin, 1997)
established multistage processes based on impregna-
tion of biomass with formic acid and introduction of
hydrogen peroxide following by addition of water and
cooking at up to 120
C for periods ranging from 60 to
180 min. This was applied to the hybrid grass Mis-
canthus  giganteus, and a comparison with native
lignin showed that the weight and number average
molecular weights (Mw and Mn) had decreased from
L IGNIN IN P OLYMER C OMPOSITES
31742 g mole1 and 2681 g mole1 to 7636 g mole1 and
1417 g mole1, respectively, as a result of the Milox
processing. In addition, the concentration of carbox-
ylic acid sites increased from 0.18 mmol ge1 to
0.35 mmol ge1 and total phenolic groups increased from
0.84 mmol ge1 to 1.31 mmol ge1, while the concen-
tration of aliphatic hydroxyl groups was reduced
from 5.54 mmol ge1 to 1.66 mmol ge1. Clearly even
organosolv processing can have significant impact on
the chemical functionality of lignins.
Alkaline conditions have also been explored in
organosolv processes. For example, the Organocell
process first impregnates biomass with a mixture
of water and methanol, or sometimes ethanol, at
temperatures of 110e140
C. Then alkali, such as
sodium hydroxide, and anthraquinone are added in
the digester where the pulping liquor, containing up
to 30% methanol by volume, is heated to 170
C at
pressures of order 10 bar for 2 h. It is thought that the
methanol may directly participate in the delignifica-
tion by forming methyl ether groups at carbocation
sites where lignin condensation could occur. This
would maintain a low-molecular weight of the lignin
fragments compared to those formed by kraft or
sulfite pulping.
2.5 Steam Explosion Lignin
(Hydrothermal Process)
The steam explosion process requires highly
compressed water, 200e2000 psi, and high temper-
ature, 180e230
C, during the short processing time
of 1e20 min in the presence of a catalyst (Wayman
and Lora, 1978, 1979, 1980; Datar et al., 2007; Zhang
et al., 2007; Ruiz et al., 2008). Hydrolysis, aryl ether
cleavage and homolytic cleavage of CeC bond,
demethoxylation, alkylation, and condensation reac-
tions occur during the steam process (Wang et al.,
2009; Kang et al., 2011). While the aromatic groups
in the lignin are not degraded by steam explosion
process, b-O-4 ether linkages and CaeCb bonds are
being cleaved during the process. The resulting lignin
has a similar character as organosolv lignin, low
molecular weight, and good solubility in organic
solvents (Wayman and Lora, 1978; Shimizu et al.,
1998). Steam explosion has great potential because
this process is the first step to produce biofuel prior to
fermentation of polysaccharide (Glasser and Wright,
1998). A few examples of lignin subunits that can be
2: E XTRACTION AND T YPES OF L IGNIN 21

Figure 3 Proposed subunits of lignin through a steam explosion (hydrothermal) process.

produced by hydrothermal process are demonstrated
in Figure 3.
2.6 Dilute Acid Lignin
Lignin can be produced by pretreatment of
biomass feedstock with various acids: sulfuric
acid (Brennan et al., 1986; Converse et al., 1989;
Thompson et al., 1992; Esteghlalian et al., 1997),
nitric acid (Brink, 1994), hydrochloric acid (Israilides
et al., 1978; Goldstein et al., 1983), phosphoric
acid (Israilides et al., 1978), oxalic acid (Chaturvedi
and Verma, 2013), and peracetic acid (Chaturvedi
and Verma, 2013). For example, dilute sulfuric acid
(0.5e1.4%) treats biomass under high temperature,
165e195
C, for 3e12 min followed by a water-
washing step (Guo et al., 2008; Ruiz et al., 2008).
The dilute acid treatment can produce lignin under
relatively mild acidic conditions with high solubility
of obtained lignin as well as low production cost
(Selig et al., 2007). The most important step of dilute
acid treatment is acid hydrolysis of raw biomass. The
acid hydrolysis let the raw biomass release mono-
meric sugars and soluble oligomers from the cell wall

Figure 4 Dilute acid pretreated biorefinery process and lignin recovery (Azadi et al., 2013; Ragauskas et al., 2014).
22
matrix to yield the porous structure of biomass
without affecting hemicellulose and lignin. The
porous hemicellulose and lignin structure offers easy
access to enzymes that may produce a biofuel
precursor, xylose and other fermentable sugars
(Mohanty et al., 2009; Chaturvedi and Verma, 2013;
Badiei et al., 2014). Following processing, the lignin
remains as a solid residue (Ragauskas et al., 2014)
(Figure 4). The overall conversion rate, however, is
quite low and the resulting lignin contains sugar
derivative impurities (Guo et al., 2008; Ruiz et al.,
2008; Mohanty et al., 2009).
3. Conclusions
The diversity of plant sources and processing
methods results in a broad range of lignins available
for use in materials applications. In addition to
established products, such as kraft lignin and
lignosulfonates, newer forms of lignin derived from
steam explosion, organosolv, or dilute acid treat-
ment broaden the range of chemical characteristics.
However, the range of molecular weight and varying
concentrations of aliphatic hydroxyl, phenolic,
carboxylate, and sulfonate groups can make lignin
choice a design variable when developing materials
based on it. Knowing the source and processing
methods provides an important starting point for
predicting the characteristics of a given lignin, and
numerous analytical methods have been estab-
lished to perform a definitive characterization.
With knowledge of these attributes, rational design
of a next generation of lignin-based materials is
possible.
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LP43932.
Etude in black. Universal City Studios, Inc. Distributed by MCA-
TV. 80 min., sd., color, 35 mm. (Columbo NBC mystery movie) ©
Universal City Studios, Inc.; 15Sep72; LP43932.

LP43933.
The Most crucial game. Universal City Studios, Inc. Distributed by
MCA-TV. 80 min., sd., color, 35 mm. (Columbo NBC mystery movie)
© Universal City Studios, Inc.; 3Nov72; LP43933.

LP43934.
Dagger of the mind. Universal City Studios, Inc. Distributed by
MCA-TV. 106 min., sd., color, 35 mm. (Columbo NBC mystery
movie) © Universal City Studios, Inc.; 26Nov72; LP43934.

LP43935.
A Stitch in crime. Universal City Studios, Inc. Distributed by MCA-
TV. 80 min., sd., color, 35 mm. (Columbo NBC mystery movie) ©
Universal City Studios, Inc.; 9Feb73 (in notice: 1972); LP43935.

LP43936.
Requiem for a falling star. Universal City Studios, Inc. Distributed
by MCA-TV. 80 min., sd., color, 35 mm. (Columbo NBC mystery
movie) © Universal City Studios, Inc.; 19Jan73 (in notice: 1972);
LP43936.

LP43937.
Double shock. Universal City Studios, Inc. Distributed by MCA-TV.
80 min., sd., color, 35 mm. (Columbo NBC mystery movie) ©
Universal City Studios, Inc.; 23Mar73 (in notice: 1972); LP43937.

LP43938.
The Most dangerous match. Universal City Studios, Inc.
Distributed by MCA-TV. 80 min., sd., color, 35 mm. (Columbo NBC
mystery movie) © Universal City Studios, Inc.; 2Mar73; LP43938.

LP43939.
5 fingers of death. Warner Brothers, Inc. 104 min., sd., color, 35
mm. Prev. pub. 22Nov72. NM: translation, revision & additions. ©
Warner Brothers, Inc.; 21May73 (in notice: 1972); LP43939.

LP43940.
Night chase. Cinema Center 100. 120 min., sd., color, videotape (2
inch) Based on a story by Collier Young. Appl. au: Cinema Center
Films. © Cinema Center Films; 16Nov70; LP43940.

LP43941.
The Romans—life, laughter and laws. Learning Corporation of
America. Made by John Secondari Productions, Ltd. 23 min., sd.,
color, 16 mm. © Learning Company of America, a division of
Columbia Pictures Industries, Inc.; 28Jul71; LP43941.

LP43942.
Summer wishes, winter dreams. Columbia Pictures & Rastar
Pictures, Inc. Released by Columbia. 93 min., sd., color, 35 mm. ©
Persky-Bright Associates; 21Oct73; LP43942.
LP43943.
A Step out of line. Cinema Center Films. 120 min., sd., color,
videotape (2 inch) © Cinema Center Films; 19Feb71; LP43943.

LP43944.
Honk ’em, squonk ’em, git the wampum. A CBS Television
Network production. 30 min., sd., color, 16 mm. (Dirty Sally) Appl.
au: CBS, Inc. (formerly Columbia Broadcasting System, Inc.) ©
Columbia Broadcasting System, Inc.; 4Jan74 (in notice: 1973);
LP43944.

LP43945.
Right of way. A CBS Television Network production. 30 min., sd.,
color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly Columbia
Broadcasting System, Inc.) © Columbia Broadcasting System, Inc.;
22Feb74 (in notice: 1973); LP43945.

LP43946.
Worthless. A CBS Television Network production. 30 min., sd.,
color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly Columbia
Broadcasting System, Inc.) © Columbia Broadcasting System, Inc.;
11Jan74; LP43946.

LP43947.
The Old soldier. A CBS Television Network production. 30 min.,
sd., color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly
Columbia Broadcasting System, Inc.) © Columbia Broadcasting
System, Inc.; 18Jan74; LP43947.

LP43948.
The Convict. A CBS Television Network production. 30 min., sd.,
color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly Columbia
Broadcasting System, Inc.) © Columbia Broadcasting System, Inc.;
25Jan74; LP43948.

LP43949.
A Horse of a different color. A CBS Television Network production.
30 min., sd., color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly
Columbia Broadcasting System, Inc.) © Columbia Broadcasting
System, Inc.; 1Feb74; LP43949.

LP43950.
Too long to wait. A CBS Television Network production. 30 min.,
sd., color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly
Columbia Broadcasting System, Inc.) © Columbia Broadcasting
System, Inc.; 8Feb74; LP43950.

LP43951.
All that glitters. A CBS Television Network production. 30 min.,
sd., color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly
Columbia Broadcasting System, Inc.) © Columbia Broadcasting
System, Inc.; 15Feb74; LP43951.

LP43952.
Much ado about nothing. A CBS Television Network production.
30 min., sd., color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly
Columbia Broadcasting System, Inc.) © Columbia Broadcasting
System, Inc.; 1Mar74; LP43952.

LP43953.
Wimmen’s rights. A CBS Television Network production. 30 min.,
sd., color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly
Columbia Broadcasting System, Inc.) © Columbia Broadcasting
System, Inc.; 8Mar74; LP43953.
LP43954.
I never saw the Pacific. A CBS Television Network production. 30
min., sd., color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly
Columbia Broadcasting System, Inc.) © Columbia Broadcasting
System, Inc.; 15Mar74; LP43954.

LP43955.
My fair laddie. A CBS Television Network production. 30 min., sd.,
color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly Columbia
Broadcasting System, Inc.) © Columbia Broadcasting System, Inc.;
22Mar74; LP43955.

LP43956.
The Hanging of Cyrus Pike. A CBS Television Network production.
30 min., sd., color, 16 mm. (Dirty Sally) Appl. au: CBS, Inc. (formerly
Columbia Broadcasting System, Inc.) © Columbia Broadcasting
System, Inc.; 29Mar74; LP43956.

LP43957.
The Taking of Pelham one two three. Palomar Pictures &
Palladium Productions. Released by United Artists Corporation. 104
min., sd., color, 35 mm., Panavision. Based on the novel by John
Godey. © United Artists Corporation; 20Sep74; LP43957.

LP43958.
The Godchild. A Mor-Film Fare. Produced in association with
Metro-Goldwyn-Mayer, Inc. 74 min., sd., color, 16 mm. © Metro-
Goldwyn-Mayer, Inc.; 26Nov74; LF43958.

LF43959.
The Shattered mask. An Alfra production. Produced in association
with M-G-M TV. 60 min., sd., color, 16 mm. (Medical Center) Appl.
au: Metro-Goldwyn-Mayer, Inc. © Metro-Goldwyn-Mayer, Inc.;
7Oct74; LP43959.

LP43960.
May God have mercy. An Alfra production. Produced in
association with M-G-M TV. 60 min., sd., color, 16 mm. (Medical
Center) Appl. au: Metro-Goldwyn-Mayer, Inc. © Metro-Goldwyn-
Mayer, Inc.; 21Oct74; LP43960.

LP43961.
The Prisoners. An Alfra production. Produced in association with
M-G-M TV. 60 min., sd., color, 16 mm. (Medical Center) Appl. au:
Metro-Goldwyn-Mayer, Inc. © Metro-Goldwyn-Mayer, Inc.;
28Oct74; LP43961.

LP43962.
The Bribe. An Alfra production. Produced in association with M-G-
M TV. 60 min., sd., color, 16 mm. (Medical Center) Appl. au: Metro-
Goldwyn-Mayer, Inc. © Metro-Goldwyn-Mayer, Inc.; 4Nov74;
LP43962.

LP43963.
Happy as the grass was green. Burt Martin Associates. 107 min.,
sd., color, 35 mm. Based on the novel by Merle Good. © Happy
Production Company; 15Jun73; LP43963.

LP43964.
Yetta the yenta. Crunch Bird Studios, Inc. 4 min., sd., color, 16
mm. Appl. au: Ted Petok. © Crunch Bird Studios, Inc.; 16Oct74;
LP43964.

LP43965.
 Pay the twenty dollars. Tandem Productions, Inc. 30 min., sd.,
b&w, 16 mm. (All in the family) © Tandem Productions, Inc.;
6Mar74; LF43965.

LP43966.
Mike’s graduation. Tandem Productions, Inc. 30 min., sd., b&w, 16
mm. (All in the family) © Tandem Productions, Inc.; 13Mar74;
LP43966.

LP43967.
Archie feels left out. Tandem Productions, Inc. 30 min., sd., color,
16 mm. (All in the family) © Tandem Productions, Inc.; 9Jan74 (in
notice: 1973); LP43967.

LP43968.
We’re having a heat wave. Tandem Productions, Inc. 30 min., sd.,
b&w, 16 mm. (All in the family) © Tandem Productions, Inc.;
12Sep73; LP43968.

LP43969.
Edith finds an old man. Tandem Productions, Inc. 30 min., sd.,
b&w, 16 mm. (All in the family) © Tandem Productions, Inc.;
26Sep73; LP43969.

LP43970.
Archie the gambler. Tandem Productions, Inc. 30 min., sd., b&w,
16 mm. (All in the family) © Tandem Productions, Inc.; 10Oct73;
LP43970.

LP43971.
Henry’s farewell. Tandem Productions, Inc. 30 min., sd., b&w, 16
mm. (All in the family) © Tandem Productions, Inc.; 17Oct73;
LP43971.