CELLULOSE CHEMISTRY AND TECHNOLOGY

PURIFICATION AND CHARACTERIZATION

METHODS FOR LIGNIN BIOMASS AS A POTENTIAL PRECURSOR FOR
CARBON MATERIALS

KATIA SANTOS DAMACENA NUNES* and LUIZ CLAUDIO PARDINI**

*
Aeronautic Institute of Technology – ITA, Marechal Eduardo Gomes Sq.,
50 Vila das Acácias, São José dos Campos, Brasil
**
Aeronautics and Space Institute – IAE/AMR, Marechal Eduardo Gomes Sq.,
50 Vila das Acácias, São José dos Campos, Brasil
✉ Corresponding author: K. Santos Damacena Nunes, katiadamacen@hotmail.com

Received June 22, 2018

A purification process has been optimized for eucalyptus and sugarcane lignins in order to meet the specification
requirements for obtaining high-quality carbon materials free of contaminants. Fluorescence XR was used to determine
the inorganic content, comprising Ca, Fe, Al, Si and Na. The ash content after the purification process met the
minimum requirements for use as a precursor of carbon materials. Elemental analyses were used to determine the
contents of C, N, H, S and O. Fourier transform infrared (FTIR) spectroscopy and the second derivative analysis were
used to determine the levels of guaiacyl, syringyl and intramolecular hydrogen interactions. FTIR, thermogravimetric
analysis (TGA) and differential scanning calorimetry (DSC) showed that sugarcane lignin has higher thermal stability
and intermolecular interactions than kraft lignin. Carbon-13 nuclear magnetic resonance (13C NMR) spectroscopy was
used for the quantitative determination of structural chemical groups and contaminants. The results indicated a large
potential for the application of the obtained lignins as precursors for carbon materials.

Keywords: kraft lignin, sugarcane lignin, purification, characterization

INTRODUCTION
Biomass is a key feedstock for the renewable By definition, lignin is a random, amorphous
production of fuels, chemicals and energy.1 ̶ 4 polyphenolic three-dimensional polymeric
Lignin is a renewable resource derived from network, with a weight-average molecular weight
biomass. It is an aromatic heteropolymer mainly (Mw) of 2400. It is a highly aromatic and highly
found in the secondary wall of wood cells. It is polymerized substance that does not possess a
the most abundant and important polymeric uniform, homogenous and well-defined
organic substance in the vegetable kingdom, after structure.9 ̶ 11,26 However, it consists of well-
cellulose.5 ̶ 8 Recently, it has been shown that established repeating units of precursors (i.e.,
lignin can potentially be a valuable low-cost coniferyl alcohol, sinapyl alcohol, p-coumaryl
precursor material for the production of high- alcohol). In Figure 1, the most common phenolic
performance carbon materials, such as carbon monomers from lignin are presented. Because of
fibers.9,10 Lignin can be obtained from various such heterogeneity, it is not possible to associate a
sources. The most abundant source for this defined structure to lignin, although some
material comes from the cellulose kraft process representative models have been proposed.12 ̶ 14
(paper mills). Recently, a new abundant source of All over the world, a large amount of biomass
lignin, based on the sugarcane bagasse process, waste is available, which represents a great
has attracted the attention of many researchers.15 potential for lignin production. In the case of
The focus, in this work, is on kraft and sugarcane wood processing for papermaking, the main by-
lignins to be used in the production of carbon product is black liquor. In the case of sugarcane
materials. lignin, the by-product is bagasse. In the first case,
lignin is obtained by chemical treatments from

Cellulose Chem. Technol., 53 (3-4), 227-242(2019)

KATIA SANTOS DAMACENA NUNES and LUIZ CLAUDIO PARDINI

black liquor, usually through a process named Composites account for only about 1 percent
LignoBoost.15,16 In the second case, the lignin of the total structural materials market by volume.
obtained is called grass lignin.15 Other Therefore, there are many opportunities to
pretreatment methods have been developed in the increase their usage in various other industries by
last decades to obtain lighter, higher-quality replacing traditional materials, such as steel and
lignin. However, some of the associated aluminum.22 For lightweight transportation
challenges arise from the recalcitrant nature of vehicles, carbon fiber, in the form of composite
lignocelluloses, including cellulose and material, is a logical alternative.23
hemicellulose, which are closely linked to lignin, Lignin has been studied since the 1970s as a
making it difficult to obtain pure lignin.17 suitable precursor for carbon fiber.24 However,
Processes such as autohydrolysis, soda and only recently, it has gained substantial attention as
organosolv are methods that strongly affect the a low-cost source for a wide range of carbon
physicochemical properties of lignin.18 Other materials, especially carbon fibers.10,25 Typical
alternatives would be those based on enzymatic specifications of lignin to be used as a precursor
systems, such as cellulolytic enzymatic lignin for carbon fiber require 1.0% by weight of ashes
(CEL) and enzymatic mild acidolyses lignin at 800 oC, volatile material less than 5% by
(EMAL), which have been considered as having weight at 250 oC and absence of coarse particles
higher yield and lower degradation.18 A variety of with the diameter greater than 1 µm.8,27 Besides,
pretreatment methods have been developed, but previous lignin studies reviewed the uses of a
only a few have reached the marketing stage. The variety of lignin types and lignin polymer blends
membrane process, mainly ultrafiltration (UF) as precursors for carbon fiber.20 The matter has
and nanofiltration (NF), has been used in pulp and been the subject of many works around the world,
paper mills since the late 1960s. Increased since the legislation stipulates low fuel
demands for environmental protection, energy consumption in the transportation industry,
savings and recovery of valuable products have recyclability and low-cost raw materials as
accentuated the need to obtain a lignin suitable for mandatory requirements.9
the different industrial proposals.19 The present work had the objective of studying
The annual world lignin production is over 70 kraft and sugarcane lignins to be used as
million tons and 95% is burned for energy precursor raw materials for achieving carbon-
generation. The remaining 5% is used for other based materials. First, a test was performed using
commercial applications, including additives, kraft lignin, without the use of any purification
dispersants, binders or surfactants.16 process, in the preparation of polymeric
There is a growing interest in the development blends.18,23,34 The preliminary results indicated
of high performance carbon materials, particularly that the lignin would not be suitable for this
carbon fibers, produced directly from biomass application because of the large amount of debris,
materials, due to the availability of these materials sugar, ashes and inconsistent particle sizes.
and their low cost.13,20 Nowadays, high- Different particle sizes in the lignin composition
performance carbon fibers are produced from would not provide an adequate material to be used
polyacrylonitrile (PAN).9,21 However, PAN is too for obtaining polymeric blends. Then, better
expensive for large-scale use in massive volume methods of purification were investigated, in an
markets, such as transportation applications, attempt to find a way to obtain lignins suitable for
restricting their usage to the aerospace, wind the intended application. One of the objectives of
energy and marine markets.9 Currently, PAN is this study was to investigate methods for lignin
produced from petroleum feedstock. It is well purification that would make it possible to have a
known that petroleum has a volatile market in low-cost precursor material suitable for the
terms of price stability and availability. Therefore, production of polymeric blends. Other objectives
alternative precursor sources are interesting to of this work included the characterization of the
investigate for use as raw materials for carbon kraft and sugarcane lignins as suitable biomass
fibers.9 materials that could be used to provide sustainable
carbon fiber precursors.

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Figure 1: Most common monolignols in lignin (H: p-coumaryl alcohol; G: coniferyl alcohol;
S: sinapyl alcohol)9─11

Figure 2: Lignin purification scheme

EXPERIMENTAL quantification of the elements was EDTA (LECO,

Materials USA), with the following contents: carbon (%):
Kraft lignin and sugarcane lignin were used in this 41.07±0.13; hydrogen (%): 5.5±0.03; nitrogen (%):
work. The kraft lignin is a hardwood lignin that was 9.56±0.02.
obtained from eucalyptus, by using the LignoBoost
process,22 and was purchased from Fibria S.A. The Methodology
sugarcane bagasse lignin (sugarcane lignin) is a grass Lignin purification
type lignin that was obtained from alkaline The lignin (kraft and sugarcane) was purified in
processing,10 and provided by CNPEM (Centro order to proceed with the characterization steps. The
Nacional de Pesquisa em Energia e Materiais). purification follows the scheme shown in Figure 2.
Chemicals, such as NaOH (IMPEX, product number Both kraft and sugarcane bagasse lignin started from a
20105IQBC) and H2SO4 (ULTRA, product number brown powder material. In a container of 30 L, 500 g
QX19522), were used in the purification process. The of lignin powder was placed, followed by the addition
quantification of C, N, H, S and O content in the lignin of 25 L of distilled H2O. Under vigorous stirring,
samples was performed using a calibration curve with NaOH was added until a pH of 12.
minimum requirements for the correlation coefficient After complete dissolution of the lignin, filtration
(r2) greater than 0.99 for the reference analytical was accomplished for removal of particulates and
standard. The analytical standard used for impurities larger than 1 µm. Then, under vigorous
quantification of the contained sulfur was petroleum stirring, H2SO4 was added to the filtrate until pH = 2,
coke (LECO, USA), with the following contents: in order to precipitate the whole filtered lignin. The
sulfur (%): 5.67±0.14; volatile (%): 13.0±0.70; ash precipitated lignin, in the form of a gel, was allowed to
(%): 0.27±0.06. The analytical standard used for stand for 24 h. Afterwards, the precipitated lignin was

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KATIA SANTOS DAMACENA NUNES and LUIZ CLAUDIO PARDINI

placed on a sturdy filter to be washed until pH 4.5-5.0 incineration of the sample at 1450 oC. Detection was
was reached. At pH = 5, the washed sugarcane and accomplished in the IR mode.
kraft lignins were placed in an oven at a temperature of
60 oC for a week. Purified and dried lignin was kept in Fourier transform infrared spectroscopy
a suitable container to avoid moisture absorption. Fourier transform infrared spectroscopy was used
for the characterization of the purified kraft lignin and
Lignin milling sugarcane lignin used in this work. In the case of
The purified lignin underwent a milling process, in lignins, Fourier transform infrared spectroscopy
a Marconi hammer mill. The purified lignin powder (FTIR) can characterize the functional groups,
was added to the hammer mill in batches of small allowing to determine different amounts of guaiacyl
amounts. After milling, the powder passed through a (G) and syringyl (S) groups. Infrared spectra of the
sieve of one hundred mesh (0.15 mm) to separate the purified kraft and sugarcane lignins were taken using
powder from larger lignin particles. The larger the Fourier transform infrared/universal attenuated
particles returned to the milling process. After the total reflectance (FTIR/UATR) technique, with 120 N
milling process, all purified lignin passed through a and 20 scans at room temperature. Measurements were
sifting process. Sieves of 200 mesh (0.074 mm) were recorded on a Perkin Elmer 20 PG. The second
used. derivative spectra from FTIR were used to determine
different types of noncovalent interactions of lignins,
X-Ray fluorescence and were also useful for the determination of the
X-ray fluorescence analysis was used in order to number of hidden peaks. All the data were analyzed
find out the content of contaminant elements in the raw and compared on the basis of the peak areas performed
materials. Samples of kraft lignin and sugarcane lignin by maximum likelihood peak fitting. Deconvolution
were analysed after the purification process. The was performed using the Gaussian shape and a full
equipment used for the analysis was the PANalytical- width at half maximum (fwhm) of 20-40 cm-1 was
Axios, Tube: Rh, power: 2.5 W; software: Super Q taken to ensure the resolution of the peaks without
manager. Samples were prepared by pressing into overfitting and a good selection of the peaks as a
tablets. measure of spectral intensity. The noncovalent
interactions explain the differences in thermal and
Determination of ash content in lignin mechanical properties between hardwood lignin and
Determination of ash in lignin was done using an sugarcane bagasse lignin.6,27,28,38,39 FTIR analysis was
EDG CON 3P model 3000 oven and the weight was done in the transmittance mode. Values for absorbance
recorded on a Mettler Toledo balance, model AB265- (A) can be obtained from the percent transmittance by:
S/Fact. Initially, the porcelain crucible was pyrolysed A = 2 - log10 (%T).
at 800 oC for two hours and cooled in a desiccator
under vacuum at room temperature. Approximately 2 g Thermal analysis by DSC and TGA
of lignin was weighed in the porcelain crucible. The Thermogravimetric analysis (TGA) has been
lignin was initially pyrolysed at 300 oC for one hour widely used to evaluate the thermal decomposition
and then the temperature was raised to 800 oC and process of solid-state materials.41 In this work, the
maintained at this level for two more hours. After the thermal properties of lignins were investigated by
calcination was completed, the porcelain crucible using thermogravimetric analysis (TGA) and
containing the ash was cooled in a desiccator under differential scanning calorimetry (DSC). The thermal
vacuum at room temperature and the sample was stability and the carbon yield of the lignin samples
weighed. were determined on a TGA from TA Instruments.
TGA results were obtained under nitrogen atmosphere
Elemental analyses in a temperature range from room temperature (RT) to
Elemental analyses were conducted on a CHN 628 1000 oC, at a heating rate of 20 oC/min. DSC scans
(LECO) for Module S and 628S (LECO) for module were obtained on a Perkin Elmer apparatus, Pyris
CHN. The detection mode for N was thermal Instruments, run from room temperature to 250 oC, at a
conductivity and for S, C and H the detection mode heating rate of 20 oC min-1 under nitrogen atmosphere.
was IR. Oxygen gas was used to burn all the raw The samples were hermetically sealed in aluminum
materials and helium was used for gas drag. The pans.28 These experiments were carried out on ~6-8 mg
elemental analysis of C, N and H was done by samples heated in an inert environment, so as to inhibit
weighing 0.100 g of raw materials and completely any secondary reactions due to fragments, such as
incinerating them at 1050 oC. The oxygen content was HCN, CO, NH3 released in the combustion process.28
obtained by difference according to the guidelines of The glass transition temperature (Tg) was recorded as
Bech et al.29 and Protásio et al.30 The elemental the midpoint temperature of the heat capacity transition
analysis for sulfur was done by weighing ± 0.1000 g of on the first heating run.
the sample in a porcelain crucible and by complete

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1D 13C NMR sugarcane lignin is much higher than that in kraft

Nuclear magnetic resonance spectroscopy (13C lignin. Therefore, a lower amount of
NMR) is useful to identify the interaction of contaminants, as shown by kraft lignin, is more
molecules, providing a detailed quantitative favorable for the use of the material as precursor
determination of the amounts of the different structural
for obtaining carbon materials.15,33
units in lignin.29,30 For recording NMR spectra, the
samples were prepared by accurately weighing pre-
dried lignin and dissolving it in deuterated Ash content of lignins
dimethylsulfoxide-d6 (DMSO-d6). Typical sample Before purification, the ash percentage at 800
o
concentrations were of the magnitude of ~200 mg cm-3 C for the kraft lignin was 1.07 wt% and for the
for the lignin samples. The 13C RMN analysis was sugarcane lignin it was 1.72 wt%. In addition,
carried out in Bruker 400 Top Spin equipment, version both lignin types showed high content of coarse
2.1 (Bruker BioSpin GmbH). The module of “Solvent- particles with the diameter above 1 µm. After the
Detect” was used within a “Top Spin” designed to purification process, the ash analysis at 800 oC
allow the spectrometer to detect and subsequently lock indicated 0.06 wt% for the kraft lignin and 0.09
on the solvent.29
wt% for the sugarcane lignin. The specifications
for lignin proposed as precursor for carbon
RESULTS AND DISCUSSION materials require an ash content below 1.0 wt% at
X-ray fluorescence 800 oC.8,27 Both lignin types have ash contents
X-ray fluorescence results are shown in Table
lower than 1.0% at 800 oC, volatile material lower
1 for kraft lignin and in Table 2 for sugarcane
than 5% at 250 oC and no content of dross
lignin. Metal contaminants in the lignins were
particles with the diameter above 1 µm. The ash
recorded and the results are shown in relation to
content analysis showed that the lignin
ash content by weight. The type and quantity of
contaminant content, after the purification
contaminants give an idea about the history of
process, is lower than 0.1 wt%. Therefore, the
salts and minerals that were absorbed by the plant
kraft and sugarcane lignins correspond to the
during the period of growth. X-ray fluorescence
specifications with regard to ash content for use
results revealed the following inorganic
as precursors for carbon materials, including
contaminants in kraft lignin: Ca, Fe, Na, Al and
carbon fibers.
Si, while in sugarcane lignin the contaminants
were: Ca, Si, Fe, Mo, Ti, Al, Na, Cl, Cu, Cr, Zr
and P. The content of contaminant elements in

Table 1
Content of inorganic elements in kraft lignin

Compound Concentration (%)

Ca 0.02
Fe 0.01
Na 0.01
Al 0.01
Si 0.01

Table 2
Content of inorganic elements in sugarcane lignin

Compound Concentration (x10-2%) Compound Concentration (x10-2%)

Si 2.7 Mo 0.25
Fe 2.5 Na 0.12
Ti 1.2 Cr 0.12
Al 1.2 Ca 0.06
Cl 0.38 Zr 0.06
Cu 0.25 P 0.06

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KATIA SANTOS DAMACENA NUNES and LUIZ CLAUDIO PARDINI

Table 3
Elemental analysis of kraft lignin (ash content: 0.06% at 800 °C)

Sample N (%) C (%) H (%) O (%) S (%)

Sample 1 0.15 62.74 5.86 26.90 2.19
Sample 2 0.12 62.24 5.88 27.36 2.24
Sample 3 0.12 62.10 5.87 27.54 2.22
Average 0.13 62.36 5.87 27.27 2.21

Table 4
Elemental analysis of sugarcane lignin (ash content: 0.09% at 800 °C)

Sample N (%) C (%) H (%) O (%) S (%)

Sample 1 0.58 58.42 6.11 31.40 0.13
Sample 2 0.58 58.25 6.15 31.54 0.13
Sample 3 0.56 58.04 6.18 31.74 0.13
Average 0.57 58.20 6.15 31.56 0.13

Elemental analysis 27.27%, while for sugarcane lignin they were: C

The lignin structure is dependent on wood = 58.20%, H = 6.15%, N = 0.57%, S = 0.13% and
species and processing conditions. Commercially, O = 31.56%. Oak Ridge National Laboratory has
lignin is obtained as a by-product of “wood free” published the necessary requirements for suitable
papermaking.40 Elemental analysis is used to raw materials to obtain lignin for use as precursor
study the structure of lignin and to determine the for carbon materials. One requirement is that the
content of C, H, N, S and O.15 In Tables 3 and 4, minimum carbon content must be above 40%.23
the results of the elemental analysis are shown. Therefore, both lignin types showed satisfactory
According to Bech et al.29 and Protásio et al.,30 carbon contents. According to the obtained
the oxygen concentration in a raw material can be results, the kraft lignin contains 62.5% carbon and
found after the determination of the concentration sugarcane lignin contains 58.2%. Comparing both
for all other element contents (C, H, N, S and lignins, the higher the carbon content, the more
ashes). appropriate is the lignin to be used as carbon
Table 3 shows that the kraft lignin used in this material precursor. Therefore, kraft lignin has
work has around 62% carbon in its molecule, higher potential to be employed for this
followed by about 27% oxygen. The carbon application.
content has great importance, since it substantially
affects the efficiency of carbon production after Characterization by FTIR/UATR-120N
the heat treatment process. On the other hand, FTIR/UATR analysis is a universal sampling
sugarcane lignin has around 58% carbon in its method for simple IR spectroscopic analysis. It
molecule, followed by 31.5% oxygen. These has a great advantage over other probe analyses
values are similar to those found for the kraft because the sample preparation is much easier,
lignin, despite the different origins of the since it requires only a good contact between the
materials. Comparing the results obtained for the sample and the top plate crystal. Besides, this
kraft and sugarcane lignins with the ones reported technique allows reading a large number of
in the work of Marin,15 it is possible to conclude samples in a short time. For lignin samples, the
that the results are quite similar. FTIR/UATR technique is more advantageous
The analyzed samples of kraft and sugarcane because the samples are analyzed without
lignins also showed the following characteristics: interference from previous preparation. Lignin
nitrogen amount less than 0.6% by weight; carbon samples are analyzed as dried powder. The
amount less than 63% by weight, hydrogen infrared spectra obtained for the kraft and
amount around 6% by weight and oxygen amount sugarcane lignins are presented in Figure 3. The
nearly 30% by weight (with a slightly lower level peak positions of the bands in the FTIR spectra
for kraft lignin when compared with that for are summarized in Table 5 for the lignin samples,
sugarcane lignin). The percentage amounts found based on literature data.6,27
for kraft lignin were the following: C = 62.36%, As sugarcane lignin is a grass type lignin, its
H = 5.87%, N = 0.13%, S = 2.21% and O = FTIR spectra show typical softwood lignin

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assignments: a band at 1270 cm-1 and 1219 cm-1 cm-1), and peaks corresponding to C-H stretching
assigned to C-O of guaiacyl ring, a band at 1120 of the methyl and methylene group (ν ~ 2842-
cm-1 related to aromatic C-H in-plane deformation 3000 cm-1) and the methyl group of methoxyl (ν ~
in the guaiacyl ring, a band at 1030 cm-1 assigned 2689-2880 cm-1). The most characteristic
to C-O deformations of secondary alcohols and vibrations of lignins correspond to those of
aliphatic ethers and a band at 915 cm-1 assigned to aromatic rings at approximately 1600 cm-1, 1513
C-H out-of-plane in positions 2, 5 and 6 (G units). cm-1 and 1420 cm-1.6,27
Softwood lignin, often referred to as guaiacyl The lignin composition could be studied by the
lignin, is mainly composed of coniferyl alcohol ratio between syringyl and guaiacyl products
units (p-coumaryl), which make up more than (S/G). This parameter is used to differentiate
95% of the structural units in this lignin. On the between softwood lignin composed of the
other hand, for hardwood lignins, there is an guaiacyl unit and hardwood lignin composed of
assignment at 1323 cm-1 related to C-O of the guaiacyl and syringyl units.43 The ratio between
syringyl ring and a band at 1111 cm-1 assigned to the band intensities at 2919, 1270 and 915 cm-1
aromatic C-H deformation in the syringyl ring. for sugarcane lignin and between the band
Hardwood lignin is composed of coniferyl alcohol intensities at 2937, 1323 and 912 cm-1 for kraft
and sinapyl alcohol derived units in varying lignin was used for determining the differences in
proportions, and is commonly referred to as the guaiacyl (G) and syringyl (S) groups. The
guaiacyl-syringyl lignin.39 results are presented in Table 6 and show the
The composition of arboreal wood depends differences in the quantities of S and G groups
mainly on the tree taxonomy and the that were determined for both lignins.38 The
environmental factors of the tree growing region. results shown in Table 6 for sugarcane lignin
The lignin of softwood trees is composed of reveal a composition made only of G units. On
guaiacyl units, whereas that of hardwood contains the other hand, kraft lignin is composed of a
both guaiacyl and syringyl moieties.43 mixture of S and G units, where S units
Based on the FTIR spectra of the sugarcane predominate. For sugarcane lignin, the results
and kraft lignins, both of them showed typical show similarity with softwood lignin as it consists
bands. Both lignin samples presented a broad only of guaiacyl propane (G units).39
band attributed to OH stretching (ν ~ 3412-3460

Figure 3: FTIR spectra obtained for kraft lignin (top) and sugarcane lignin (bottom)

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KATIA SANTOS DAMACENA NUNES and LUIZ CLAUDIO PARDINI

Table 5
IR vibrational band assignments for kraft lignin and sugarcane lignin

Kraft lignin (hardwood) Sugarcane lignin (grass)

Wavenumber (cm-1) Assignment Wavenumber (cm-1) Assignment
829 ν (-CH) guaiacyl 833 ν (-CH) guaiacyl
δ ,ν (CH) out-of-plane in δ ,ν (CH) out-of-plane in
912 915
positions 2, 5 and 6 (G units) positions 2, 5 and 6 (G units)
ν (C-O) ester δ (CH) aromatic ring in
1029 1030
ν (C-C) aromatic methoxy groups
1111 ν (C-O) 1120 δ (CH) in guaiacyl units
ν (C-C; C-O; C=O) phenolic ν (C-C; C-O; C=O) phenolic
1211 1219
groups groups
- - 1270 C-O guaiacyl ring
Vibration S ring and G
1323 C-O of the syringyl ring 1327
condensed
Vibration aromatic ring; δ
1423 Vibration aromatic ring; δ (CH) 1422
(CH)
1455 δ (C-H; CH3; CH2) 1461 δ (C-H; CH3; CH2)
1513 Vibration aromatic ring 1506 Vibration aromatic ring
1600 ν (C-C; C=O) aromatic 1595 ν (C-C; C=O) aromatic
1698 ν (C=O) carbonyl 1691 ν (C=O) carbonyl
δ (CH) in methyl and δ (CH) in methyl and
2839 2849
methylene units methylene units
ν (C-H) methyl and methylene ν (C-H) methyl and methylene
2937 2919
groups groups
3399 ν (OH) alcoholic and phenolic 3385 ν (OH) alcoholic and phenolic

Table 6
Ratio of intensities from absorbance level showing differences in the amount of guaiacyl and syringyl groups present in
sugarcane and kraft lignins

Sugarcane lignin Kraft lignin

(A) 1270/2919 (A) 915/2919 (A) 1323/2937 (A) 912/2937
1.44±0.06 0.52±0.06 1.80±0.04 0.59±0.03
G units G units S units G units

Hydrogen bonding, which is a noncovalent properties. The assignments for free hydroxyls in
interaction, plays an important role in the thermal alcoholic groups are in the spectrum range of
and mechanical properties of biopolymers such as 3640-3616 cm-1. Other bands related to
lignins. Complex hydrogen-bonding systems intramolecular hydrogen bonds in phenolic groups
present in lignin, grass and hardwood have strong occur between 3560-3550 cm-1. Intermolecular
interactions. This reduces the thermal molecular hydrogen bonds to phenolic groups and their
motion of the lignin molecules and could explain combinations with alcoholic groups occur
the differences in glass transition temperatures.38 between 3520-3480 cm-1. Multiple formations of
According to Kubo and Kadla,38 the hydroxyl intermolecular hydrogen bond to phenolic groups
groups in alcoholic and phenolic compounds form and their combinations with alcoholic groups are
several intermolecular and intramolecular in the range of 3416-3390 cm-1. Intermolecular
hydrogen bonds. The response bands of lignins hydrogen bonds between biphenols and their
can be better identified by the second derivative combinations with alcoholic groups occur
spectra of the FTIR. Figures 4 and 5 show the between 3242-3238 cm-1. Multiple formation of
bands assigned to intermolecular and an intermolecular bond in biphenols is found in
intramolecular hydrogen bonds that could explain 3219 cm-1. In the range of 3191-3165 cm-1,
the little differences between kraft and sugarcane multiple formation of an intermolecular hydrogen
lignins as regards thermal and mechanical bond between biphenol and other phenolic groups

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is observed. The results of the analysis of the several types of C-C bonds, which likely behave
second derivative curves indicate that sugarcane as cross-links between the relatively short, linear
lignin has higher complexity and band intensity chains of phenyl-propane units. These linkages
than kraft lignin. The band intensity value for will affect the degree of condensation because
hardwood lignin is nearly half of the value for they allow a more complex macromolecular
sugarcane lignin and the spectrum exhibits lower network structure. Hardwood lignins possess
complexity. Therefore, FTIR analysis of grass and guaiacyl and syringyl propane in their structures,
hardwood lignin revealed differences in the exhibiting a less complex hydrogen-bonding
intensity of inter hydrogen bond formation. system than softwood.38,39 These characteristics
Aliphatic hydroxyl groups form stronger could explain the reason why sugarcane lignin is a
hydrogen bonds than phenolic hydroxyl groups. little more stable and has a higher Tg value than
In softwood lignins, the linkage between kraft lignin.
guaiacyl-propane units predominates and there are

Figure 4: Second derivative FTIR spectra in the 4000-3000 cm-1 range for kraft lignin (syringyl + guaiacyl)

Figure 5: Second derivative FTIR spectra in the 4000-3000 cm-1 range for sugarcane lignin (guaiacyl)

Table 7
Band positions and wavenumber shifts (∆νO-H) for the lignin bands obtained from second derivative FTIR spectra

Band position (cm-1) ∆νO-H (cm-1)

Sugarcane Kraft Sugarcane Kraft
3650 3640 265 241
3620 3610 235 211
3560 3550 175 151
3550 3540 165 141
3480 3475 95 76

The average strength of the intermolecular wavenumber shift (∆νO-H) between the free
interactions could be estimated by the hydroxyl-stretching vibration and that of

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KATIA SANTOS DAMACENA NUNES and LUIZ CLAUDIO PARDINI

hydrogen-bonded species, related to the center of distance values for the lignins were determined,
the hydroxyl band. The wavenumber shift (∆νO-H) and sugarcane lignin showed values slightly
can be calculated for kraft lignin as ∆νO-H = |3399 greater than those of kraft lignin.
- νO-H|, and for sugarcane lignin as ∆νO-H = |3385 -
νO-H|, as shown in Table 7.39 The interactions Thermal characterization of kraft and
between hydroxyl groups in sugarcane lignin are sugarcane lignins by TGA and DSC
stronger than in kraft lignin. This can be Thermal characterization by TGA
associated with the higher thermal stability and The thermal behavior was characterized by
higher energy activation (Ea) observed for thermogravimetric analysis. The weight losses of
sugarcane lignin by thermogravimetric analysis. lignins were described by the recorded TG/DTG
Therefore, a higher amount of energy is necessary (differential thermogravimetric) curves. Figures 6
to break the hydrogen bonds inter sugarcane and 7 show the TG and DTG curves for hardwood
lignin groups and this shows that this type of kraft lignin and sugarcane lignin. When lignin is
lignin is more stable. exposed to elevated temperatures, significant
The ∆νO-H values could be obtained from the physical and chemical changes related to
bands assigned to phenol groups by a linear variations in weight, dehydration and oxidation of
relationship between the enthalpy of hydrogen specimens as a function of temperature and time
bond formation and the OH wavenumber shift, occur.5 The thermal degradation of hardwood
according to the relation: kraft lignin and sugarcane lignin is shown in
-∆H (kcal/mol) = 0.016 ∆νO-H + 0.63 (1) Figures 6 and 7. The analysis indicates that the
thermal degradation and the maximum rate of
The ∆νO-H values obtained from the bands
weight loss are observed at 334 oC for kraft lignin
assigned to phenolic groups in lignin at 3560 cm-1
and at 342 oC for sugarcane lignin. The weight
and 3550 cm-1 were used to determine the
loss is observed in the range between 150 oC and
enthalpy of bound hydrogen. The hydrogen bond
1,000 oC. A weight loss of nearly 40% was found
distances (R) for the two bands described before
for both lignins up to 1,000 oC. These results are
were obtained according to an equation proposed
very close to those reported by Poletto, for kraft
by Pimentel and Sederholm:39
lignin and softwood lignin.39
R = 2.84 - ∆νO-H /4430 (2) Both thermogravimetric analyses show a wide
The enthalpy of hydrogen bond formation temperature range for thermal degradation,
between phenolic groups is higher in the observed from 100 oC to 1,000 oC. The thermal
sugarcane lignin than in the kraft lignin, as shown stability of the lignins can be explained by the
in Table 8. The distances of hydrogen bonds in amount of aromatic rings, different functional
sugarcane lignin are lower than those in kraft groups and chemical bonds. Syringyl and guaiacyl
lignin. Thus, the donor and acceptor atoms in the units compose the lignin macromolecules. Ether
O-H•••O hydrogen bond in sugarcane lignin are bonds build these units, and the bonds between
closer than in kraft lignin. Therefore, the syringyl units are easier to split than those
interactions between both atoms are more intense between guaiacyl units. This may contribute to
in the sugarcane lignin, which results in stronger higher thermal stability and higher activation
intermolecular interactions, higher wavenumber energy for the grass lignin, which consists only of
shift and higher enthalpy with respect to the -OH guaiacyl propane G units, compared to hardwood
groups. These results reveal an important aspect lignin, which is basically composed of syringyl-
of sugarcane lignin thermal stability.38,39 The propane units (S units).39
enthalpy of -OH groups and the hydrogen bond

Table 8
Enthalpy (-OH) wavenumber shift and hydrogen bond distance values for the lignins studied

-∆H (kJ/mol) R (nm)

Lignin samples
3560 cm-1 3550 cm-1 3560 cm-1 3550 cm-1
Sugarcane 14.36 13.69 2.80 2.80
Kraft 12.77 12.14 2.81 2.81

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 Lignin

Figure 6: TGA and DTG curves of kraft lignin in the temperature range of 25-1,000 oC
and heat rate of 20 oC/min

Figure 7: TGA and DTG curves of sugarcane lignin in the temperature range of 25-1,000 oC and
heat rate of 20 oC/min

Figure 8: DSC curves of kraft lignin (weight = 5.7 mg; temperature rate of 20 oC/min; N2 atmosphere)

It can be seen from the TG/DTG curves that range of 300-650 oC, which is the result of the
the degradation process for these materials has formation of products such as CO, CO2,
three stages. In the first stage, which occurs at benzaldehyde and phenol. In the third stage, when
temperatures lower than 300 oC, a relatively low the temperatures are above 650 oC, strong
percentage of weight loss, mainly due to the dehydration occurs, and the carbon-link structure
release of absorbed water and aldehydes, is is thus gradually formed, generating CO as a by-
observed.24 The second stage occurs within the product.24

237
KATIA SANTOS DAMACENA NUNES and LUIZ CLAUDIO PARDINI

Figure 9: DSC curves of sugarcane lignin (weight = 7.4 mg; temperature rate of 20 oC min-1; atmosphere N2)

Thermal characterization by DSC atoms of carbonyl groups. The second region,

Figures 8 and 9 show the differential scanning which is bounded by 165-100 ppm, is related to
calorimetry (DSC) analysis for the kraft lignin aromatic and olefin carbon atoms. The third
and sugarcane lignin. Endothermic and region, which extends between 100-20 ppm, is
exothermic events, along with glass transition related to aliphatic carbon atoms (α, β, γ and
changes, were obtained.5 methoxyl).36,37 Freitas et al.44 published a study
The DSC analysis of kraft lignin and about the 13C NMR analysis of rice hull
sugarcane lignin reveals a distinct endotherm biomass.44 The sugarcane lignin in our study and
around 80 oC in the first heating stage, which the rice hulls had almost the same characteristics
results in a Tg of 81.3 oC for kraft lignin and a Tg because they were not submitted to a strong
of 82.3 oC for sugarcane lignin, which is cellulose extraction process, such as kraft lignin.
recognized as a Tg characteristic of a natural Residues of cellulose and hemicelluloses were
polymer. Lignin is moderately stable at elevated identified. A parallel was made between the kraft
temperatures due to its highly aromatic backbone and sugarcane lignins and the rice hull biomass.
and has a very interesting thermal behavior Cellulose and hemicellulose residues were
because it can act as a thermoplastic as well as a identified in both samples. Besides, the kraft
thermoset.33 However, in the second stage of lignin showed a lower quantity of these residues
heating, no significant event was found up to 200 than the sugarcane lignin. The main structures
o
C. The disappearance of Tg in the second stage studied by 13C NMR are shown in Figure 10,
can happen if lignin undergoes self- where a polymer backbone of lignin is shown,
polymerization and cross-linking during the first with the groups of -OCH3, Cα, Cγ and Cβ and the
stage of heating. In this way, lignin turns into a cellulose backbone with the carbons identified.
thermoset material.33 Pucciariello et al. analyzed Figure 11 shows the 13C NMR spectrum of
the DSC curves (obtained by heating from 60 oC kraft lignin and Table 9 shows the signal
to 200 oC at a rate of 20 oC min-1) and reported assignments for the 13C NMR peaks of kraft lignin
that the Tg obtained was around 60 oC.33 The and sugarcane lignin. In the spectrum from Figure
difference between the results could be explained 11, it is possible to identify residues of cellulose
by the effect of chemical structures on the thermal and hemicellulose. The content of cellulose
properties of lignins. According to Kadla,41 the residues is around 5.8% by weight, with signals
glass transition temperature for hardwood lignin centered at 73.2 and 84.7 ppm. In the region of C1
is 83.3 oC. For sugarcane lignin, no result is – cellulose, there is a superposition with more
provided in the literature. intense signals corresponding to C-2/C6 in S
lignin (a broad signal centered at 104.9 ppm, and
1D 13C NMR characterization a content of 8.7% by weight). Hemicellulose
NMR provides an easy tool for the residues display peaks centered at 18.8 ppm (with
characterization of several functional groups, 1.0% by weight) and at 174.0 ppm (with 1.2% by
including acid and methoxyl groups, phenolic and weight). Methoxyl groups (-OCH3) show 16.9%
aliphatic units. The 13C NMR spectrum can be by weight and a corresponding signal centered at
divided into three main regions. The first region, 55.7 ppm. Aromatic regions represent 41.2% by
delimited around 200-165 ppm, covers the carbon weight, with corresponding signals between

238
 Lignin

113.5-156.2 ppm. Specifically, C1 syringyl and characterized basically by G and S structures, and
C1 guaiacyl correspond to 20.7% by weight and C4 and C5 carbons are related to G units, with the
their signals are centered at 137 ppm, and the prevalence of guaiacyl and syringyl units in the
signals of C3 and C4 guaiacyl are located at 147.5 lignin. The presence of cellulose has also been
ppm.42 The aromatic region of kraft lignin is observed between 89-71 ppm. Compounds like
between 97-156 ppm. The C3/C5 S carbons cellulose products are referred to as
appear at 152.8 ppm and 115 ppm. C3 carbons are contaminants.34,35

Figure 10: Structures of lignin and cellulose biomass analysed by 13C NMR (S corresponds to syringyl lignin and G
corresponds to guaiacyl lignin)41

Table 9
Signal assignments for 13C NMR of kraft lignin and sugarcane lignin33,39

Chemical shift (ppm) Assignments for kraft and sugarcane lignin

>172 C-OOR
168 Cγ
139-155 Aryl C-OR
152.2 C-3/C-5, S
148-149.2 C-3, G
144-145 C-4, G
123-139 Aryl C-R
138 C-4, S
134 C-1 S and C-1 G
130 C-2/C-6, H
125 C-1, PC/PC ester
122 C-6
119 C-6, G
115 C-3/C-5
111 C-2, G
103-104 C-2/C-6, S
96-117 Aryl C-H
~83 Cβ
~76 Cα
~69 Cγ
49-65 -OCH3, S and G
30 Aliphatic (α/β-methylene in propyl side chains

239
KATIA SANTOS DAMACENA NUNES and LUIZ CLAUDIO PARDINI

Figure 11: 1D 13C NMR spectra of kraft lignin

Figure 12: 1D 13C NMR spectra of sugarcane lignin

The main signal assignments for 13C NMR of hemicellulose residues appears at 172.3 ppm with
sugarcane lignin are shown in Figure 12 and 2.6% by weight.
Table 9. The region at 30 ppm corresponds to Although not illustrated in the spectra of
aliphatic chains, their content being around 9.09% Figures 11 and 12 for kraft and sugarcane lignins,
by weight. The region at 49-70 ppm is attributed the populations of carbonyl groups and aryl ether,
to -OCH3, with a content of 22.17% by weight. condensed aryl, aryl, aliphatic side-chain related
The region between 70-90 ppm corresponds to Cβ, to Cα, Cβ, and Cγ carbons, methoxy and aliphatic
Cα and Cγ, with 3.61%, 2.45% and 4.80% by carbons are identified at ~172, 141-152, 123-140,
weight, respectively. In this region, the resonance 110-123, 83-61, 55 and 30 ppm, respectively (see
lines are superimposed on a signal of cellulose Table 9).36,37,44
residue. The region between 100-111 ppm
corresponds to aryl C-H, with the content of CONCLUSION
6.57% by weight. The region between 110-120 After the purification process, kraft lignin and
ppm corresponds to -C in guaiacyl, with the sugarcane lignin were verified to be suitable as a
content of 8.50% by weight. Guaiacyl (G) renewable raw material for manufacturing carbon
residues were verified by the signals at 153.7 ppm materials. The results from the analyses have
(C-3, G) with 4.4% by weight, 147.9 ppm (C-4, shown that the investigated lignins are in
G) with 6.1% by weight, and 134.3 ppm (C-4, G) accordance with the required specifications for
and 130.2 ppm (C-1, G) with 14.1% by weight. the use in processes to obtain precursors for
More guaiacyl signals can be observed at 116.3 carbon materials. The results obtained for ash
ppm (C-6, G) with 8.5% by weight and at 106.3 contents are 0.06% for the kraft lignin and 0.09%
ppm (C-2, G) with 6.5% by weight. A for the sugarcane lignin. The volatile material is
superposition of the resonance lines due to C1 below 5% at 250 oC and no dross particles with
cellulose residues and C-2 from guaicyl residues the diameter above 1 µm were found. Both types
is observed.36,42,44 A signal corresponding to of lignin have high carbon content: kraft lignin

240
 Lignin

9
showed 62.36% and sugarcane lignin – 58.20%. K. S. D. Nunes, L. C. Pardini and N. P. Alves,
The second derivative FTIR spectra showed that Procs. 2nd Brazilian Conference on Composite
the intermolecular and intramolecular interactions Materials – BCCM2, September 15-18, 2014.
10
between the hydroxyl groups in sugarcane lignin J. L. Braun, K. M. Holtman and J. F. Kadla,
Carbon, 43, 385 (2005),
are stronger than in kraft lignin. This behavior
https://doi.org/10.1016/j.carbon.2004.09.027
supports the higher thermal stability and higher 11
A. N. Zabaleta, PhD Thesis, Escuela Politécnica de
activation energy observed for sugarcane lignin. San Sebastian Donostiako/Eskola Politeknikoa, 2012.
Analyses by 13C NMR provided a picture 12
M. Funaoka, React. Funct. Polym., 73, 396 (2013),
about the composition of kraft and sugarcane https://doi.org/10.1016/j.reactfunctpolym.2012.05.010
13
lignin and also showed cellulose contaminants. X. Xie, B. Goodell, D. Zhang, D. C. Nagle, Y. Qian
The results of all the analyses of kraft lignin et al., Bioresour. Technol., 100, 1797 (2009),
revealed values typical for hardwood, and those https://doi.org/10.1016/j.biortech.2008.09.057
14
of sugarcane lignin showed characteristics of S. Kubo and J. F. Kadla, Biomacromolecules, 4,
softwood lignins, in spite of the fact that 561 (2003), https://doi.org/10.1021/bm025727p
15
G. C. Q. Marín, PhD Thesis, Universidad Pontifica
sugarcane is a grass.
Bolivariana, Medellín, 2009.
The final consideration is that the evaluated 16
S. Laurichesse and L. Avérous, Progress Polym.
lignins have a great potential to be used as raw Sci., 39, 1266 (2014),
material precursors for the production of valuable https://doi.org/10.1016/j.progpolymsci.2013.11.004
17
carbon materials, such as carbon fiber, based on K. Servaes, A. Varhimo, M. Dubreuil, M. Bulut, P.
their availability, sustainability, low cost and high Vandezande et al., Ind. Crop. Prod., 106, 86 (2017),
carbon yield. doi.org/10.1016/j.indcrop.2016.10.005
18
A. García, M. G. Alriols, G. Spigno and J. Labidi,
ACKNOWLEDGMENTS: The authors would Biochem. Eng. J., 67, 173 (2012),
like to thank FIBRIA for supplying the raw lignin http://dx.doi.org/10.1016/j.bej.2012.06.013
19
J. Chen, F. Shen, G. Lyu, G. Yang, N. Lu et al.,
used in their study. Thanks are also due to Dr.
Cellulose Chem. Technol., 52, 371 (2018),
George Jackson da Rocha of CNPEM for valuable http://www.cellulosechemtechnol.ro/pdf/CCT5-
discussions. Useful suggestions by Dr. Roberto 6(2018)/p.%20371-380.pdf
David Martinez Garcia are appreciated. This 20
D. A. Baker and T. G. Rials, J. Appl. Polym. Sci.,
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21
Aperfeiçoamento de Pessoal de Nível Superior – J. F. Kadla, S. Kubo, V. A. Venditti, R. D. Gilbert,
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