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 LIGNIN IN POLYMER
COMPOSITES

Omar Faruk
Mohini Sain

Amsterdam • Boston • Heidelberg • London • New York • Oxford

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William Andrew is an imprint of Elsevier
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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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15567030903226249.
de Wild, P.J., Huijgen, W.J.J., Gosselink, R.A., 2014.
Lignin pyrolysis for profitable lignocellulosic bio-
refineries. Biofuels, Bioproducts and Biorefining 8
(5), 645e657. http://dx.doi.org/10.1002/bbb.
de Wild, P.J., van der Laan, R.R., Wilberink, R., 2010.
Thermolysis of lignin for value-added products. In:
XV Meeting of the International Humic Substances
Society. Energy Research Centre of the Nether-
lands, Tenerife, Canary Islands, Spain, pp. 1e27.
Wu, S., Argyropoulos, D.S., 2003. An improved
method for isolating lignin in high yield and
purity. Journal of Pulp and Paper Science 29 (7),
235e240.
Zakzeski, J., Jongerius, A.L., Bruijnincx, P.C.A.,
Weckhuysen, B.M., 2012. Catalytic lignin valoriza-
tion process for the production of aromatic chemicals
and hydrogen. ChemSusChem 5 (8), 1602e1609.
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
Another random document with
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“June says you’ve had an offer for this house. Who made it, and
what’s he offered?”
Allen leaned forward to knock off the ash of his cigar on the tray
beside him.
“That’s what I wanted to see you about,” he said slowly. “Yes, I’ve
had an offer. It’s from a man named Spencer from Sacramento. Just
come down here to settle. He’s got a big family, and wants a good
sized house and garden for the kids to play in. Fashionable locality
doesn’t count for much with him. He’s offered twenty-five thousand
down for the place as it stands, furniture and all.”
There was a slight pause and the speaker added:
“It’s what decided me to go to Virginia, get rid of this—and—and—
get some ready money. I’m pretty close to the ragged edge, Jim.”
“I don’t see how it’s going to benefit you,” said the Colonel. “My
mortgage and the interest for two years back, paid in full, doesn’t
leave you much more than your fares to Virginia.”
Allen got up, walked a few steps away, then came back and stood by
the Colonel’s chair. His face was deeply flushed, but it had lost its
embarrassed air. He looked resolute and determined.
“Jim,” he said doggedly, “I’ve got to have that money.”
“Beau Allen,” said the Colonel in the same tone, “by what right do
you dare to say that to me?”
For a silent moment they eyed each other, then the elder man went
on:
“Twenty-five years ago you stole my sweetheart. Four years ago you
tried to steal my land and I gave it to you, because you had a wife
and two helpless children; and now you’re trying to steal my house.”
“I’ve got the same right as I had before,” said the other, “I’ve still got
two helpless children.”
“Am I to be robbed to provide for your children?”
“You’re using pretty strong words, Jim, but you’ve had provocation.
You’ve met bad usage at my hands and you’ve given back good.
Give it back once more, for the last time. Give it back for the sake of
my two girls. They’re as helpless now as they ever were, and God
knows I’m as unable to help them.”
“Why should I keep on providing for your children? You’re their
father, younger than I, and as able-bodied. Four years ago I put you
on your feet when I gave you the Parrish Tract. You’ve had your
chances, the best I could give you. I’m on the ragged edge too. I’m
sixty years old and I’ve had to apply for a position.”
“Listen to me, Jim,” with desperate urgence. “Let me have this
money till after Rosamund’s marriage. Let me have fifteen thousand
dollars of it. So help me God, I’ll invest the rest in your name in any
securities you mention. Don’t you see I’ve got to have money till after
that? I can’t let Harrower know we’re bust. You think he doesn’t care.
But I tell you he does. What’s going to happen to Rosamund if he
throws her over at the last moment?”
The Colonel was silent, looking at the ash tray from beneath down-
drawn, bushy brows. Allen close at his elbow continued with fevered
intensity:
“Rosamund’s wrapped up, body and soul, in that man. What’s she
going to do if he backs out? And you know him; you’ve seen the kind
he is, daft about his family and his ancient, honorable name. Even if
he doesn’t want money with her do you think he, with his ancestors’
portraits hanging on the walls, wants to marry a girl whose father’s a
busted mining speculator—in debt all round, who hasn’t got the
means to buy his daughter a decent dress to get married in? Look at
June! Are the futures of both my daughters going to be ruined
because I’m broke? Good God, Parrish, you care for them! You can’t
now, when you see what June’s been brought to, stand in the way of
Rosamund’s happiness.”
The Colonel sat looking at the ash tray for a frowning moment, then
he said:
“What have you done with the spring? If there had been no mineral
on the land the spring would have brought you an income for years.”
“I sold the land with the spring on it, after the Crown Point collapse.
Blake, the hotel man in San José, bought it, and is building a hotel
up there now. That’s the past. I’m not defending it, nor my life
between then and now. I’m talking of my children. Put me, and what I
am, out of the question. It’s my two girls that count just now.”
The Colonel rose, and walking to the fireplace, stood there with his
elbow on the mantel-piece, looking down at the small fire that glowed
in the grate. Allen by the table watched him with anxious, waiting
eyes.
“I’ve got chances in Virginia,” he said. “Living on the spot there’s a
different proposition from running back and forth like this. The
Maybough properties that I’m interested in are looking pretty
promising. Inside of a year, if they turn out as we expect, I may be
able to pay you the whole sum back.”
The Colonel gave a suppressed sound, short and scornful, but did
not raise his head. The other went on.
“Fifteen thousand will carry us to Virginia and over the wedding.
Harrower’s to be back in the spring and they’ll be married as soon as
he comes. Spencer wants the house in January or February. That
will just about fit in. We can go to Virginia as soon as the sale’s
completed and have everything ready and in shape by the time
Harrower gets here. And it will be better for June, too, better to get
her out of all this. She feels pretty bad, poor little girl! One of the
reasons that makes me so keen about selling the place and leaving
is to get her away from all this talk about Barclay and that Gracey
girl.”
The Colonel, without raising his eyes, said:
“You’ll want the whole twenty-five thousand.”
“No—no—” said Allen with undisguised eagerness, hope illuminating
his face, “fifteen will do, though of course twenty would be better.
Fifteen ought to carry us well along into the summer, and by that
time the Maybough should be paying. There’ll be the wedding and
the trousseau. Of course twenty would be better, but if you’ll let me
have the fifteen I can do it. I’ll invest the other ten any way you may
say and—”
He stopped as the Colonel turned from the fire with a short laugh.
“Sell the house,” he said, “and take it all.”
“What?—” Allen did not quite dare to believe it.
“Sell the house. See Spencer as soon as you can, and I’ll give you
satisfaction of the mortgage.”
“Jim!” the other ejaculated, and held out a shaking hand.
But the Colonel brushed by it and passed into the hall, where his hat
and coat hung. Allen followed him, trying to talk, but he stopped the
feeble words of gratitude. Standing under the hall lamp, the light
falling on his white hair, he said,
“There’s no thanks between you and me. If it wasn’t for your
daughters I’d see you standing on the corner begging for nickels and
not drop one in your tin cup. And you know it. You know, too, what I
feel about them, and why I feel it. You know I’d do it again if I had the
money. But I haven’t. There’s not much more to be got out of me.
You’ve about sucked me dry.”
The night was clear and he walked home, slowly and lingeringly by a
circuitous route of cross-streets. At first he paced onward in an
absorbed reverie, his eyes down, striking the cracks in the pavement
with the tip of his cane. Presently he looked up above the housetops,
at the widths of sky sown with great, calm stars. It was early night;
only the larger stars were visible. Once or twice as he walked on
looking up, he laughed, a short, dry laugh, at himself and the follies
he had committed.
When he reached his own room in the Traveler’s Hotel he found
Rion’s answer to his letter. Standing under the feeble light that fell
from the sitting-room chandelier he read it. It was short, for Rion was
but a poor correspondent. The position of assistant secretary of the
Cresta Plata would be vacant on January first. The Gracey boys
would be flattered if one of James Parrish’s reputation and position
would care to fill it. The salary would be five hundred dollars a
month.
The Colonel turned the letter over, eying it. The heaviness of his
spirit was lightened. Through the few lines he seemed to feel the
strong grip of the mining man’s hand, to meet the searching look of
his keen, honest eyes. They would all be together in Virginia—not
such a bad beginning for a new life at sixty.
END OF BOOK II
 BOOK III
THE DESERT
 CHAPTER I
NEVADA
The mountain wall of the Sierra bounds California on its eastern
side. It is a rampart, towering and impregnable, between the garden
and the desert. From its crest, brooded over by cloud, glittering with
crusted snows, the traveler can look over crag and precipice,
mounting files of pines and ravines swimming in unfathomable
shadow, to where, vast, pale, far-flung in its dreamy adolescence,
lies California, the garden. On the other side—gaunt, hostile, gray—
is Nevada, the desert.
In other lands nature and man have ended their struggle for
supremacy. Man has conquered and nature, after long years of
service, is glad to work for him, to quicken the seed he sows, to swell
the fruit on the branch, and ripen the heads of grain. She laps him
round with comfort, whispers her secrets to him, reveals herself in
sweet, sylvan intercourse. And he, cosily content, knows her as his
loving slave, no more rebellious, happy to serve.
But in Nevada, nature is still unconquered, savage and supreme. It is
the primordial world, with man a shivering stranger amid its grim
aloofness. When the voice of God went out into the darkness and
said, “Let there be light,” the startled life, cowering in caves and
beneath rocks, may have looked out on such a land—an unwatered
waste, treeless, flowerless, held in an immemorial silence.
Man as we know him has no place here. He is a speck moving
between the dome of sky and the floor of earth. Nature scorns him,
has watched him die and whitened his bones in a few blazing weeks.
The seed he plants withers in its kernel, the earth he turns up,
frosted with alkali, drops apart in livid flakes. The rare rivers by which
he pitches his tent are sucked into the soil, as though grudging him
the few drops with which he cools his burning throat. An outcast from
a later age he is an intruder here. These solemn wastes and eternal
hills have not yet learned to call him master.
When the pioneers trailed across it, Nevada was to them only “the
desert,” a place where the horrors of heat and thirst culminated.
They knew it as a sterile, gray expanse, breaking here and there into
parched bareness, and with lines of lilac-blue or reddish-purple hills
seeming to march with them as they moved. From high places they
saw it outspread like a map, its surface stippled with sage and the
long green ribbon of a tree-fringed river looping across its grim
aridity. At evening it took on limpid, gem-like colors. The hills turned
transparent sapphire and amethyst, the sky burned a thin, clear red.
An unbroken stillness lay upon it and struck chill on the hearts of the
little bands who, oppressed by its vast indifference, cowered beneath
its remote, unfamiliar stars.
As they passed across it they mined a little; here and there they
scraped the surface, clustered round a stream-bed for a day or two
and sent the water circling in their pans. But California, the land of
promise, was their goal. With the western sun in their eyes they
looked at the mountain wall and spoke of the Eldorado beyond
where the gold lay yellow in the sluice box, and flecked with glittering
flakes the prospector’s pan.
That was in forty-nine. Ten years later they were hurrying backward
over the mountains to the streams that drain Mount Davidson.
Nevada had its wealth too, a hidden, rock-ribbed wealth, jealously
buried. They tore it out, built a city of tents and shacks as they
delved, and in ten years more were gone again, dispersed over the
far West like the embers of a fire which a wind scatters.
Then once again the barren state drew them back. Deep in the roots
of Mount Davidson one of the greatest ore-bodies in the world lay
buried. This time they gathered in their might. Miner, engineer,
assayer, stock-jobber, manipulator, manager and millionaire poured
over the mountain wall, bringing in their train the birds of prey that
follow in the wake of the mining army. The city of tents and cabins
grew into a city of streets and buildings and spread, climbing the
mountain side in terraces. A railroad crawled perilously to it, looping
over the mountain flanks. In a cleared nook by a river the smoke of
its mills blackened the sky.
Isolated from the rest of the world, encircled by desolation, the town
seethed and boiled with an abnormal activity, a volcano of life in the
midst of a dead land. About it the desert brooded, pressing in upon
it, watching and waiting. To it the little city was an outside thing,
hostile, alien, unwelcome. It scorned the pigmy passions of its men
and women, had no sympathy with the extravagances of their money
madness. When they had been brushed away like an ant-hill by a
passing foot, it would sweep over their town, obliterate their traces,
reclaim its own. And once again the silence of a landscape where
there is neither ripple of water nor murmur of leaf would resettle in
crystal quietude.
Confined within their own walls, with no outlet for the pressure under
which they lived, the inhabitants of Virginia burned with a wild activity
and energy. The conditions of life were so unusual, so fiercely
stimulating to effort and achievement, that average human beings
were lifted from their places and became creatures of dauntless
initiative. They conquered the unconquerable, accomplished
triumphs of daring and ingenuity where under ordinary
circumstances they would have recoiled before insuperable
obstacles. They were outside themselves, larger for good or evil than
they had ever been before or would be again. Nature had dared
them to her vanquishing and they had risen to the challenge.
In the spring of 1874 the ferment incident to the opening of the great
ore-body that has gone down in history as the “Big Bonanza,” began
to bubble toward boiling point. Month by month stocks had steadily
risen, and month by month the huge treasure chamber, filled with
silver as a nut is with kernel, developed in ever-increasing richness.
The city was packed close as a hive with bees with twenty-five
thousand souls all quivering to the increasing momentum of the
excitement. The mines were a dynamo whence electric vibrations
spread into the world outside. The dwellers in huts among the sage
were shaken by them. They thrilled along the Pacific slope. In New
York and London men felt them and their pulses quickened. The
Bonanza times were nearly at the flood.
The city grew with astonishing rapidity, breathlessly climbed the side
of Mount Davidson in ascending tiers of streets. There was no time
for grading or paving. Two stories in the front meant four in the back,
the kitchens of B Street looked over the shingled roofs of the shops
on C Street. It was a gray town, clinging to a desolate mountain side,
in a gray country. At its base, appearing to force it up the slope, were
the hoisting works of the mines, dotted so close along the lode they
nearly touched. Every mine in this line was a mighty name in the
world of finance. New York, London and Paris waited each morning
to hear news from the town in the wilderness. And as the ant-hill
swarmed and trembled with the fury of its concentrated life, the
desert looked on, serene, incurious, still.
 CHAPTER II
OLD FRIENDS WITH NEW FACES
The Allen girls moved to Virginia City in April. Their father had gone
there early in the year and taken a house which would be a proper
and fitting place from which to marry Rosamund. He had found what
he thought suitable in the mansion, as they called it in Virginia, of
one Murchison, a mining superintendent, who, in the heyday of
sudden riches, had built him a comfortable home and then died.
The Murchison mansion had come on the market just at the right
moment, Allen told people. Men wondered where his money came
from, as the current talk among his kind was that “the bottom had
fallen out of the Barranca, and Allen was bust.” He himself spread
the story that successful speculations had once again set him on his
feet. That something had done so was proved by his renting of the
Murchison mansion, a furnished house in the Virginia City of that
period being an expensive luxury.
It stood at the south end of B Street, perched high on the top of two
sloping terraces which were bulkheaded by a wooden wall,
surmounted by an ornamental balustrade. Small fruit trees and
flowering shrubs clothed the terraces in a thin, flickering foliage, just
showing its first, faint tips of green when the girls arrived. A long
flight of steps ran up to a balcony which rounded out about the front
door, and upon which one seemed to be mounted high in the air,
looking down over a dropping series of flat and peaked roofs to
where the dark red walls and tall chimneys of the hoisting works
clustered about the city’s feet. Beyond this unrolled the wild, bare
landscape, undulating line of mountain beyond mountain, cut clear
as cameos against the blue Nevada sky.
The vivid green streak made by the Carson River gleamed to the
right. At the limit of sight, fitted into a gap between the hills, was the
Carson desert, a patch of stark, yellow sand.
The girls were not surprised at the style of the house. They knew
vaguely that their father’s affairs were not as satisfactory as they had
been, but of their truly desperate nature they had no suspicion.
There were delays in the sale of the Folsom Street property, and it
was not till March that the new tenant appeared from Sacramento to
take possession. In response to their father’s orders they obediently
gathered together their belongings, closed the house, and made the
move to Virginia without assistance from him.
Events had fallen together in an unexpected way, but one that in the
end spared June those glimpses of her lover’s happiness that she
had told the Colonel would be unbearable. It is true that she had to
see the carriages drive to Jerry’s marriage and hear the sound of his
wedding bells. But before that event circumstances had developed
which made radical changes in the plans of bride and groom. Black
Dan had discovered that Jerry’s business had dwindled to nothing,
his private fortune vanished in the Crown Point collapse. The
bonanza king, with his rapidly accumulating millions, had a sturdy,
American objection to an idle man, especially when that man was to
be the husband of his only child, and was known to be of a light and
pleasure-loving temperament. A position was made for Jerry on the
Cresta Plata, with duties sufficiently exacting to keep him continually
occupied, and with the added attraction of an exceedingly generous
salary.
Mercedes sulked when she heard it. She did not want to live in
Virginia. She had thought she might go there from time to time, flit
through it, a disturbing vision of beauty to miners and millionaires,
but to take up her residence there was a different matter. She
wanted to occupy the fine house her father had given her in San
Francisco, entertain royally and be a queen of society, with Jerry as
a necessary satellite circling about. She complained to Black Dan,
even cried a little, and for the first time in her life found him obdurate.
The doting father was troubled about the future of his child. He
disliked the marriage she was making, but knew that to protest
against it was hopeless. He mistrusted Jerry, whose record he had
often heard canvassed, and whose style, as a charmer of women, he
despised. He wanted the pair under his eye. He wanted to keep his
hand tight on his son-in-law. He did not believe that the man loved
Mercedes, and he took a bitter satisfaction in bringing him to Virginia
and setting him to work.
“Rion and I can watch him,” he thought to himself. “We’ll keep his
nose to the grindstone, and if he shows any symptoms of lifting it
we’ll hold it closer.”
Black Dan said little of his uneasiness to any one save his brother.
The two men had the same opinion of Jerry, and though neither
expressed it to the other, each felt cold doubts as to the happiness of
the marriage.
Early in January, after a honeymoon of less than a week, Jerry was
summoned to his new duties. He and Mercedes were installed in a
house on B Street which had been hired and hastily refitted for them.
Here in the heart of a biting Nevada winter their married life began.
Neither bride nor groom guessed that it was being surreptitiously
watched by three pairs of interested eyes. To the observation of the
suspicious and inimical Graceys that of Colonel Parrish was added.
He too had come to Virginia on the first of January to assume his
position as assistant secretary of the Cresta Plata. He and Rion had
settled themselves in comfortable quarters on the floor over
Caswell’s drug store, where their rooms gave on a balustraded
wooden veranda which looked out on the turmoil of C Street.
It was not from Jerry, but from Mercedes that the first signs of
discontent came. She had hated Virginia from the first glimpse of it.
The cold, bleak town, buffeted by furious winds, clinging to its bare
mountain side, revolted her. Her little soul shrank before the
loneliness of the silent desert. She was essentially a Southron, a
lover of sunshine, bright colors, and gaiety. Moreover, for the first
time in her life, she felt neglected. In Virginia City in 1874 there were
more engrossing interests than the allurement of women. It was a
man’s town, where the softer sex was in the background, save as a
diversion and spectacular luxury. Mercedes was often lonely. Jerry
had flung himself into the speculative fever of the time with fury.
Even Black Dan was preoccupied and abrupt. Making millions is,
after all, the most absorbing pastime that man may know.
Finally a delicacy of the throat developed, and Mercedes looked pale
and thin, and began to cough. It was April, she had been married
four months, and she wanted to go; she wanted San Francisco and
sunshine, and the amusements for which she lived.
Jerry did not protest. The dream of passion was at an end. The
Mercedes he had come to know in the intimacy of married life was
so different a being from the Mercedes who had beguiled him in the
summer, that he was not sorry to have her leave him. His pride was
hurt and he felt angry and bitter against her, but he had no poignant
regrets. Neither had loved. The ignoble instincts that had drawn
them together were satiated. Her woman’s spite had worked itself
out. His lust for her wealth, his desire for her possession, were
satisfied. They were willing to part.
She left in April, it being understood that Jerry was to “go below” to
see her every two weeks. The story that her health had been
impaired by a climate which had proved too severe for many before
her, was given out as the reason for her departure. Black Dan even
was made to believe it. He also believed her assurances that she
would return in the summer. He thought the few tears she shed were
grief at parting with a husband whom he supposed she loved. He
determined to watch Jerry closer than ever, and for this purpose
moved into the house on B Street, where the husband was now left
alone.
Thus it fell out for June that she was spared the sight of Jerry as a
joyous bridegroom. Almost simultaneously with the Allens’ move to
Virginia, Mercedes left it. June and Rosamund were arranging the
Murchison mansion on B Street when Mrs. Jerome Barclay was
beginning those extensive purchases in San Francisco which were
to render her home on Van Ness Avenue a truly “palatial residence.”
June saw her old lover often. The contracted size of the town made it
impossible for her to avoid him. More than once they encountered
each other in the houses of friends, and were forced to interchange
the little dead phrases of society. Both were shaken by these
accidental meetings. June dreaded and shrank from the sight of his
face and the sound of his voice; but Jerry went away from her
presence, stirred and uplifted, his mind full of the thought of her, his
sense of her charm reawakened.
His life, crowded with the strenuous business of men, was empty of
what had been for years its main interest and preoccupation. The
vain man, confident of his attractions, had been played with and
scornfully cast aside. The bitterness of his marriage was as
wormwood to him. He felt sore toward Mercedes, whose indifference
toward him had roused in him the angry amaze that a spoiled child
feels toward the stranger who is proof against its blandishments. He
felt himself wronged, and in a way, trapped. They made him work
like a day laborer for his salary, and his wife had left him. That was
what he’d got by marrying! Lupé, poor, dead Lupé, would not have
treated him so! And June—what a fool he’d been! He forgot that
June had no money, and for that reason he had put her resolutely
aside. He forgot that last year he had avoided her and tried to banish
all thought of her. In his longing for the adulation and tenderness
upon which he had lived her image came nearer and nearer, grew
more and more disturbing and sweet.
Early in May Rosamund left for a week’s visit to San Francisco to
accomplish the major part of her trousseau-buying. June, left in the
Murchison mansion to “keep house”—a duty which she performed
but ill—found many empty hours on her hands. She had made few
friends in the new town. The apathy which had fallen on her at the
time of Jerry’s engagement had not lifted, and the coming loss of
Rosamund weighed heavier every day. In the tumult around her her
life was quiet and colorless. She told the Colonel that he was the
only constant visitor she had.
“If you’ve another as regular as I am,” he had answered, “I’ll have to
look into it.”
Then he had added, in what he fondly thought was a light,
unmeaning tone, “Don’t even see much of Rion?”
“Rion?” June had replied with the arched eyebrows of surprised
query. “I don’t see him at all.”
After that there was nothing more to be said, except of course for the
Colonel to go to Rion and ask him why he had not called on Miss
Allen, and for Rion, red and embarrassed, to answer that he did not
suppose Miss Allen would care to see him, but if she did he would
go.
There was one house to which she did pay constant visits. This was
Mitty Sullivan’s, on the north side of town, near the Cresta Plata
hoisting works.
These were booming days for Mitty. Her husband’s fortune was
mounting in leaps too vast and rapid to be easily calculated. The
Gracey boys’ belief in their superintendent had not been misplaced.
The brawny, half-educated Irishman had risen to a commanding
position, and was respectfully alluded to as having “the best nose for
ore in the two states.” He was already very rich, having for the past
four years successfully speculated on “inside information.” His great
gains made even the princely salary he received on the Cresta Plata
seem small. He was in the thick of the whirlpool now and Mitty was
with him. She had a baby, a girl, and she saw it, backed by the
fortune that she and Barney were making, going to Europe and
marrying “a lord.” For Mitty’s horizon had widened with astonishing
rapidity since the days when she waited on table at the Foleys hotel.
On one of the afternoons of Rosamund’s absence June walked
across town for a chat and a cup of tea with her old-time friend. From
B Street and its neat house-fronts and gardens she descended to
the never-ending movement of the street below. This—the main
stem of the mining city—for ever seething with a turbulent current of
life, was the once famous C Street, a thoroughfare unique in the
history of American towns.
The day shift would not be up for hours yet. When its time was up
the mines would vomit forth thousands of men, who, penned all day
in the dark, stifling heat of the underground city, would pour into the
garish brilliancy of the overground one for the diversions of the night.
Here, in the gusto of their liberation, they would range till daylight,
restless eddies of life, passing up one street and down the other,
never silent, never still, pressing vaguely on through the noise and
glare, with the encircling blackness hanging round their little piece of
the animated, outside world, like an inky curtain.
At all hours the street was crowded. Now it stretched up its mile or
two of uneven length like a gray cañon, filled to both walls with a
human river. Under the arcade formed by a continuous line of roofs
that jutted from the second-story windows across the sidewalk, an
endless throng passed up and down. They collected in groups
before shop windows, overflowed the sidewalk and encroached on
the middle of the roadway, congested in a close packed, swaying
mass of heads in front of the bulletin boards where the stock
quotations were pasted up, gathered in talkative knots at corners.
The street, in the mud of which playing cards, bits of orange peel,
fragments of theatrical posters, scraps of silk and ribbon were
imbedded like the pattern in a carpet, was as full as the sidewalk.
The day of the overland freighters was past, but ore wagons still
drove sixteen-mule teams, the driver guiding by a single rope, the
mules bending their necks under the picturesque arches of their
bells. Between these, busy managers flashed by in their buggies,
stopping here and there to lean from their seats for a moment’s
converse with a knot of men. In more fashionable equipages,
brought up from San Francisco and drawn by sleek-skinned, long-
tailed horses, the wives of suddenly enriched superintendents lolled
back gorgeously, their beruffled silk skirts floating out over the wheel,
the light flashing on their diamonds.
Over all this movement of life there was an unceasing swell of
sound, a combination of many notes and keys, more noticeable by
reason of the outlying rim of silence. Thousands of voices blended
into a single sonorous hum, through which broke the jingling of
pianos from the open doors of saloons, the click of billiard balls, the
cries of the drivers to their mules, the raucous voices of street
hawkers selling wares at populous corners, and the sweet, broken
melody of the bells. Beneath this—a continuous level undertone—
was the murmur of machinery, with the faint throb of the engines
beating through it like the sound of the steady, unagitated pulse-
beats of a laboring Titan.
June pressed through the throng, walking rapidly toward the upper
end of C Street. Here, looking down on the dark red walls and tall
chimneys of the Cresta Plata, stood the pretty, one-story cottage
where Mitty Sullivan lived. It was surrounded by a square of garden,
in which lilacs were budding and apple-trees showed a delicate hoar
of young blossom. Mitty’s prosperity revealed itself in many ways.
She had a nurse for the baby as well as a “hired girl.” She was
exceedingly anxious to spend money and very ignorant of how to do
it. She had passed the stage—a recognized station in the ascending
career of the western wife—where her husband had presented her
with diamond ear-rings. The silver, crystal, and Britannia metal in the
superintendent’s cottage were astonishing; only to be rivaled in
extravagance by the dresses which hung in Mitty’s own wardrobe
and which had been ordered—regardless of cost—from the best
dressmakers in San Francisco.
She greeted June with affection and drew her into the parlor, recently
furnished with a set of blue and gold brocade furniture, the windows
draped with lambrequins to match. There was a brilliant moquette
carpet on the floor and the walls were hung with oil paintings, which
Barney had bought on a recent visit to the coast. A quantity of
growing plants in the windows added a touch of beauty to the
glaring, over-furnished room.
Mitty herself had grown into a blooming matron, a trifle coarse, for
she was fond of “a good table” and saw to it that her hired girl knew
how to produce one, and already menaced by the embonpoint which
is so deadly a foe to Californian beauty. The baby girl on her arm
was a rosily healthy infant, with Barney’s red hair and her mother’s
freshness of color. Twenty years later she would bring her share of
the Bonanza fortune, which her father was then accumulating, to the
restoration of the old New York family into which she was to marry.
Her sister—yet unborn—was to do the same charitable act by the
castle and estates of an English earl, who in return would make her
a countess.
The greetings over, the baby was placed by the table in her high
chair and given a string of spools and a rubber rabbit to play with,
while Mitty, comfortably settling herself in an arm-chair, inquired if
June had noticed the stock quotations on her way down. The hired
girl, who was setting down the tea tray, listened with open attention
for the answer. Both mistress and maid were “plunging” according to
their means, and when June confessed that she had passed the
bulletins without reading the figures, the two speculators looked at
each other in open dismay.
“It’s so long to wait till Barney comes home,” Mitty complained. “I
thought of course you’d read them as you passed.”
June was contrite, but could remember nothing.
“And I wanted to know so much! They say that Peruvian’s getting
soft. They were saying so this morning anyway. You didn’t even hear
anything as you came along? I believe you’re the only woman in
Virginia who doesn’t speculate.”
June had not even heard. The knowing volubility of Mitty on the
fluctuations of stocks in which she was as well versed as Barney
himself, seemed little short of miraculous to the only woman in
Virginia who didn’t speculate.
The servant, who had been eagerly listening to the conversation,
now broke in.
“I’ll run up and have a squint round, Mrs. Sullivan. Maybe I can pick
up more than Miss Allen.”
Mitty tried to be dignified and give the proposition a deliberate
consideration. But her consent came with a promptitude it was
difficult to suppress. As the woman whisked out through the kitchen
door she said in a tone intended to excuse her lack of discipline:
“That girl’s got all her money in Peruvian, and hearing it was ‘soft’
has sort of upset her. Last week she told me she was thirty thousand
dollars ahead. She only came to live with us because Barney being
one of the big superintendents, she thought she’d get points, and as
she’s an A 1 girl I’ve got to humor her.”
They chatted over their tea, Mitty regaling her guest with the gossip
of the day, of which she was full. They had been talking some time
when the conversation turned on Mercedes and Jerry. It was the first
time the subject had come up between them. Mitty knew part at least
of her friend’s story, and she had tried to spare her, but she hated
Mercedes, who had treated her with scornful indifference, and she
hated Jerry because Barney did. She was glad now to give her
candid opinion to the woman they had combined to hurt.
“They said it was her health that was bad, and that was why she had
to quit and go below. Health!” with a compressing of the corners of
her mouth and a glance of sidelong meaning. “Her health’s all right; it
was her temper.”
“Temper!” said June faintly. “Uncle Jim said her throat was delicate
and she had a cough.”
“Cough!” snorted Mitty. “We all have coughs, but we don’t leave our
husbands and go cavorting down to San Francisco to throw round
money and pick up some other man. She didn’t care for him. That
was all that was the matter. It’s a simple disease and a lot of ’em get
it.”
June silently stirred her tea. Every word pierced her, but she wanted
to hear them. She had heard nothing of the separation, except the
generally accepted story of Mercedes’ delicate health. Instinct told
her that Mitty, the woman, had looked deeper and would know more
of what had really been the case. Without speaking she raised her
eyes from the cup and fixed them on the baby, who in an excess of
affection was licking the face of the rubber rabbit. Mitty went on with
complacent volubility:
“Barney thought maybe it was a baby. He’s a simple, innocent sort of
man, Barney Sullivan. But I said to him, ‘Don’t you fear, there won’t
be any babies in that house! The Lord ain’t goin’ to make such a
break as to give that woman a baby.’ I guess not,” said Mitty, folding
her arms and looking grimly round the room as if challenging an
unseen audience to contradict her.
June returned to the stirring of her tea while her hostess continued,
“No. She just hated Virginia. Nobody was standing round here to kiss
her boots and do the doormat act. And she didn’t like Jerry well
enough for him to make her stand it. You have to like a man a good