Methacrylated Kraft Lignin As A Double Edged Sword A Quantitative Analysis of Kraft Lignin Containing Objects Printed by Stereolithography

Methacrylated Kraft lignin as a double-edged sword:
a quantitative analysis of Kraft lignin-containing
objects printed by stereolithography
Stephen C. Chmely,1* Mostafa Rohi Gal,1 Aditi Arya,1 Wei-Shu Lin,1 Gamini P. Mendis2
1
Department of Agricultural and Biological Engineering, The Pennsylvania State University,
University Park, PA 16802 USA
2
School of Engineering, Penn State Behrend, Erie, PA 16563 USA
KEYWORDS Kraft, lignin, 3D printing, stereolithography, additive manufacturing
ABSTRACT Finding an alternative to fossil-based resins which is renewable, sustainable, and
affordable is an important step to enable large-scale industrial manufacturing using
stereolithography. Lignin has shown some potential to fulfil these requirements. However,
examples that contain Kraft lignin, which is produced industrially at a rate of 70 million tons per
year, are relatively scarce compared to examples using organosolv lignin or lignin model
compounds. In this work, we fractionated and modified Kraft lignin and blended it with a
commercially available stereolithography resin produce 3D printed objects. We thoroughly
characterized the lignin, the resins, and the 3D printed objects, and conclude that while our
modification scheme allows for smooth incorporation of large amounts Kraft lignin into resins (up
https://doi.org/10.26434/chemrxiv-2023-klv3z ORCID: https://orcid.org/0000-0002-2637-9974 Content not peer-reviewed by ChemRxiv. License: CC BY-NC-ND 4.0
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to 10% (w/w), or 10 times the amount previously demonstrated as possible), and the lignin itself
aids in the photopolymerization process (Ec = 662(2) mJ·cm-2 for the base case, Ec = 0.763(1)
mJ·cm-2 for resins containing 10% (w/w) lignin), the printed objects are weaker (σ = 20(1) MPa)
and more brittle (ε = 1.12(5)%) than the control that contains no Kraft lignin (σ = 46.3(5) MPa,
ε = 3.95(9)%). Together, these results demonstrate the importance of lignin modifications to create
miscible blends for stereolithography resins but highlight the need for further understanding how
these modifications can simultaneously enhance photo- and mechanical properties of printed
objects. These are an important first step towards creating 3D printable objects that contain
industrially relevant lignin.
2
INTRODUCTION
Additive manufacturing by 3D printing is an effective and innovative way to fabricate materials
compared to conventional manufacturing processes. It allows users to efficiently produce materials
with complex structures.1 One of the major 3D printing techniques, stereolithography printing
(SLA) creates solid objects by free radical photopolymerization of liquid resins which are cured
layer by layer by UV light.2 However, a major hinderance for moving SLA printing to industrial
scale is the existence of inexpensive photoactive resins. Accordingly, a large body of research is
focused on developing new photoactive resins with interesting combinations of properties.3
The performance properties of liquid resins and printed objects are strongly correlated to the
components included in the resin formulation, which include reactive diluents, oligomers, UV
blockers, and photoinitiators. In addition, various carbon nanomaterials, including graphene oxide,
nanocellulose, and carbon nanotubes have been used as reinforcing additives to improve the
mechanical and thermal properties of the printed objects.4–6 Since many resulting combinations
are not environmentally or economically sustainable, a growing need exists to find sustainable
alternatives to mitigate the environmental concerns brought about by using fossil-based resources
for industrial 3D printing.7
Lignocellulosic materials are known as the most abundant and renewable materials in the world.
Lignin is the second most abundant natural polymer after cellulose,8 and it is produced industrially
as a byproduct in pulp and paper industries. Unfortunately, only 1-2% of 70 million tons of lignin
produced is used to generate valuable products,9 and the remainder is combusted to generate low-
value process heat.10 Rapidly emerging environmental issues related to non-renewable petroleum
products has brought lignin to the forefront as a precursor to high-value biorenewable products.11–
14
3
Unsurprisingly, lignin has been widely investigated as a component in various 3D printing
precursors.5,15 Investigations focused on using lignin in multicomponent resins for 3D printing by
SLA or other vat-polymerization techniques are vastly outnumbered by those using other 3D
printing technologies.16 Some examples of well-characterized resins containing phenolic
monomers that could be isolated from lignin exist.17–19 Although these examples demonstrate the
potential utility of lignin for additive manufacturing, isolating discrete molecules (e.g. vanillin,
guaiacol, etc.) from heterogenous technical lignin (e.g. Kraft, organosolv, etc.) is exceptionally
challenging from both an engineering and economic standpoint, and itself is the focus of a
tremendous amount of research.20
Instead, incorporation of technical lignin, such as Kraft or organosolv, is emerging as a method
to valorize these industrially relevant lignin samples without the separation costs incurred through
isolating discrete monomers. Whole technical lignin can be modified directly by acylation with,
e.g., methacrylic anhydride, which allows it to be incorporated into photoactive resins for 3D
printing. Our group has recently demonstrated that both hardwood21 and softwood22 organosolv
lignin can be modified and incorporated into 3D printing resins, and these resins display enhanced
performance properties because of the lignin present.
Isolation of discrete small molecules perhaps represents the most challenging and expensive
route for lignin valorization via 3D printing. In contrast, direct incorporation of Kraft lignin (the
most widely available and industrially relevant technical lignin sample available today), without
chemical modification, represents the least technically challenging and (potentially) most
ecologically friendly option. However, results using unmodified technical lignin in 3D printing
resins are mixed.
4
For example, cellulose nanomaterials coated with 3-6% (w/w) lignin have been shown to greatly
enhance the mechanical and thermal performance of 3D printed composites.23,24 The presence of
lignin in these composites likely increases the matrix-fiber interactions between hydrophilic
cellulose nanomaterials and hydrophobic SLA resin mixtures.25 On the other hand, attempts to
incorporate unmodified Kraft lignin into a commercial SLA resin led to only a modest increase in
mechanical properties, and the total amount of lignin contained in these resins did not exceed 1%
(w/w).26 Given our success with chemical modification of organosolv lignin for incorporation into
3D printer resins, coupled with the wide availability of industrial Kraft lignin, we set out to
investigate how chemical modifications of Kraft lignin would affect the performance properties of
objects 3D printed from resins that contain it.
In this contribution, we modified fractionated Kraft lignin using the methacrylation strategy we
employed for organosolv lignin. We then then blended this material with a commercial SLA resin
and measured performance properties of the resin and objects 3D printed from it. We have shown
that the modifications act as a kind of “double-edged sword,” whereby they allow for a much
greater amount of lignin to be incorporated into resins, and have potentially beneficial effects on
resin photoproperties, but the mechanical properties of objects printed from them do not enjoy the
same improvements as those printed using organosolv lignin. We speculate on the reasons for this
behavior and present some potential solutions below.
MATERIALS AND METHODS
Reagents
Indulin AT softwood Kraft lignin was provided by the WestRock Company, Atlanta, GA USA.
It was fully characterized as described below. SainSmart Rapid UV General Purpose
Photopolymer Curing Resin (405 nm, transparent) was purchased from Amazon.com, Inc. 2-
5
chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (TMDP), methacrylic anhydride
(MilliporeSigma, Burlington, MA USA), chloroform-d, and dimethyl sulfoxide-d6 (Cambridge
Isotope Laboratories, Inc., Tewksbury, MA USA) were stored in a desiccator over anhydrous
calcium sulfate prior to use. Ultrapure water (specific resistance, ρ = 18.18 MΩ⋅cm) was used for
all preparations. All other reagents were used as received from their respective vendor unless
otherwise noted.
Lignin fractionation and preparation
Acetone fractionation of Kraft lignin was conducted as described elsewhere.27 Briefly, the parent
technical lignin was separated into two fractions using a concentration of 10% (w/v) suspension
of lignin in acetone. This mixture was allowed to stir at ambient temperature for 24 h.
Subsequently, the dissolved (low molecular weight, MW) fraction was separated from the solid
(high MW) fraction by filtration through a cellulose filter paper. The filtrate was collected, and the
low-MW lignin isolated by evaporating the solvent in a rotatory evaporator followed by drying
under vacuum at ambient temperature for 24 h. The high-MW precipitate was rinsed with acetone
followed by drying under vacuum at ambient temperature for 24 h.
The as-fractionated low-MW lignin was suspended in 0.2 N H2SO4 and stirred at ambient
temperature for 1 h to remove extractives or other industrial impurities. The material was
subsequently filtered, suspended in water at 70 °C, shaken, and centrifuged three times to remove
any traces of sulfuric acid. The fractionated and washed low-MW lignin was used for all
subsequent experiments unless otherwise noted.
Lignin characterization
Gel permeation chromatography was performed using a 1260 Infinity High Temperature GPC
System (Agilent Technologies, Santa Clara, CA, USA) equipped with a refractive index (RI)
6
detector. The instrument and reference cell flow rates were set to 1 mL/min and all analysis and
calibration were performed in tetrahydrofuran (THF, HPLC grade, Sigma Aldrich, St. Louis, MO,
USA). A PL gel Mixed-C column (5 µm particle size, 7.5 x 300 mm, Agilent Technologies) was
used to perform the separation. A 200-µL injection volume and a run time of 15 minutes were used
for all samples. The molecular weights were calibrated using polystyrene standards with a range
of molecular weights from 128 Da to 2 MDa (EasiVial PS Tri-Pack, Agilent Technologies, Santa
Clara, CA, USA) were used to calibrate the system. Lignin samples were dissolved in THF at 40
°C for 1 hour before performing analysis. All lignin samples were acetylated prior to analysis
following a procedure described elsewhere.28
Hydroxyl (OH) group content of the lignin samples was measured by phosphitylation using
31
TMDP followed by P NMR spectroscopy using a Bruker Avance 500 spectrometer. Samples
were prepared using ~30 mg lignin. Sample preparation, data collection, and processing were
performed as described elsewhere.29
FTIR spectra were obtained using a Bruker Vertix 70 spectrometer equipped with a liquid
nitrogen cooled MCT detector. All samples were run in attenuated total reflection at an incident
angle of 45 degrees. A total of 500 scans were averaged at 6 cm-1 resolution and absorbance was
calculated by referencing to the clean bare crystal.
Lignin modification
The protocol for lignin acylation was adjusted from our previous method applied for
modification of organosolv hybrid poplar lignin.21,22 Briefly, 5 g lignin (8.2 mmol hydroxyl groups
per g lignin, 41 mmol OH total) was suspended in 110 mL 1,4-dioxane. To this suspension was
added 8.7 mL methacrylic anhydride (59 mmol, 1.4 equiv) and 0.24 g dimethylamino pyridine
(DMAP, 1.96 mmol, catalytic). The resulting mixture was heated to 60 °C and stirred for 48 h,
7
after which time it was allowed to cool to ambient temperature and quenched with saturated
aqueous sodium bicarbonate. The precipitated modified lignin material was isolated by
centrifugation and washed with water until the washing liquid had a neutral pH. The isolated
methacrylated lignin (M-lignin) was then dried at 40 °C under vacuum for 48 h and ground to a
friable powder using a mortar and pestle.
Resin formulation and characterization
M-lignin was weighed and added to a known amount of SainSmart Rapid UV general purpose
photopolymer curing resin to generate 30-g batches of composite resins containing 1, 2, 5, and
10% (w/w) M-lignin. The formulated resins were mixed in a Thinky ARM-310 planetary mixer
(THINKY USA, Laguna Hills, CA USA) at 2000 rpm for 30 min to obtain uniform mixtures. The
final formulated resins were transferred into firmly sealed opaque white polypropylene containers
to protect them from light prior to printing.
Rheological properties of the formulated resins were measured using a TA Instruments
Discovery HR-3 hybrid rheometer (TA Instruments, New Castle, DE USA) with a cone and plate
geometry. The rheometer was configured with a 40-mm diameter cone at a truncation gap of
48 µm. Tests were performed by varying the shear rate from 0 to 100 Hz at 20 °C.
3D printing and mechanical testing
All objects were printed using an Elegoo Mars 2 PRO Mono LCD MSLA Resin 3D Printer
(Elegoo, Inc., Shenzhen, Guangdong, China). The build platform was calibrated according to
instructions provided by the manufacturer before each print. Printed objects included working
curve windowpanes21,22 and ASTM D638 Type-IV tensile testing specimens.30 CHITUBOX
(CBD-Tech, Shenzhen, Guangdong China) was used to set up the printing parameters for each
object.
8
All printed objects were soaked in an acetone bath at ambient temperature for 2 min to ensure
all uncured resin was removed. After drying with a stream of compressed air, objects were post-
cured with a 400-W metal halide UV lamp (Uvitron International, Inc., West Springfield, MA
USA) with an irradiance of 200 mW/cm2. Objects were irradiated for a total of 1 minute and
inverted halfway through the process to ensure complete curing of both sides.
Ultimate tensile strength, Young’s modulus, and strain at break of the printed and post-cured
objects were measured using an Instron 5567 dual column universal testing machine (Instron,
Norwood, MA USA). A 30-kN static load cell was used according to the ASTM standard D63830
(Type IV specimen dimensions) with a 1 mm/min extension rate for all tests. Each property was
measured and reported as an average of at least 4 replications.
Statistical analyses
All measurements are reported as the mean of at least 4 replications. However, given the small
number of samples collected, a non-parametric Kruskal-Wallis one-way analysis of variance was
employed to determine if any statistical difference exists between the groups followed by a post-
hoc Mann-Whitney U test (95% confidence level) of the null hypothesis.31
RESULTS AND DISCUSSION
Lignin preparation, modification, and characterization
Given that Indulin AT is a softwood Kraft lignin from an industrial pulping process, we wanted
to ensure that we were working with clean material that was free of residual sugars or other process
reagent residues. In addition, we were interested in isolating low-MW material so that it would be
maximally soluble in the 3D printer resin that we chose for these studies. Accordingly, we used a
previously reported molecular weight fractionation using acetone, followed by a washing step
9
using dilute sulfuric acid. This fractionation process allowed us to isolate 20% (w/w) of the lignin
as low-MW material.
We used size exclusion chromatography to analyze the molecular weight distribution of the
lignin samples before and after fractionation, the results of which are summarized in Table 1.
Table 1. Molecular weight distributions of parent Kraft and fractionated lignins.
Sample Mn (g/mol) Mw (g/mol) Ð
Kraft lignin 2684 3257 1.213
High-MW lignin 2717 3313 1.219
Low-MW lignin 1959 2135 1.09
As shown in Table 1, fractionation of Kraft lignin using acetone produces a lignin fraction with
a lower weight- and number-average molecular weight and a tighter dispersity. This is an important
result, since lower molecular weight lignin typically has a higher solubility in conventional organic
solvents, due primarily to the lower degree of branching and chain entanglement occurring in low-
MW lignin.32 We hypothesized that this enhanced solubility would be beneficial regarding
dispersion of the suitably modified lignin material in photoactive hydrophobic 3D printer resins.
Accordingly, we modified this low-MW lignin using methacrylic anhydride as demonstrated in
Scheme 1 below.
Scheme 1. Modification of softwood Kraft (primarily guaiacyl-type) lignin with methacrylic
anhydride.
10
The modification using methacrylic anhydride necessarily produces methacrylic acid as a
byproduct of this reaction (Scheme 1, red molecules). This material needs to be removed by
neutralization and thorough washing, although raising the pH of lignin suspensions could also
catalyze the dissolution of lignin. Moreover, the atom economy of such a modification, which
produces a mole of acidic byproduct for every mole of hydroxyl group substituted, is not
particularly attractive for an industrial process. Still, recycling of this material and reformation of
the anhydride from it could be relatively straightforward and would have a beneficial effect on the
carbon footprint of this process. These investigations are ongoing in our laboratory.
Because the modification reaction targets aliphatic and aromatic hydroxyl groups of lignin, 31P
NMR spectroscopy and FTIR spectroscopy would be ideally suited to characterize the resulting
modified Kraft lignin (M-lignin). Figure 1 summarizes the results of these spectroscopic
investigations.
11
Figure 1. (a) Fourier-transform infrared (FTIR) spectra of Kraft lignin (top, brown), fractionated
and rinsed low-MW Kraft lignin (middle, blue), and methacrylate modified M-lignin (bottom,
31
green). (b) P NMR spectra of the same samples (color scheme and position identical) with
integration ranges.
The FTIR spectra of the various lignins (Figure 1a) reveals a reduction in intensity of the peak
associated with –OH groups in lignin (3404 cm-1). This is due to the substitution of the
methacrylate groups at free hydroxyl groups as depicted in Scheme 1 above. Moreover, the FTIR
spectra show increasing intensities of peaks associated with C=O bond stretches (ν = 1723 cm-1),
C–O–C asymmetric stretches (ν = 1131 cm-1), and in-plane =CH2 scissoring bends (δ = 943 cm-1)
in M-lignin, all associated with the addition of the methacrylate moiety onto lignin.21
In addition, 31P NMR spectroscopy is a method used to quantify the amount of hydroxyl groups
and can be used to determine differences among substitutions at the aliphatic and aromatic
hydroxyl groups in lignin. As expected for softwood lignin, the 31P NMR spectrum (Figure 1b)
shows an abundance of G-type aromatic hydroxyl groups, with a vanishingly small amount of
groups associated with S- and H-type lignin.33 We measured a total hydroxyl group content of 8.2
12
mmol OH per g lignin, which we used to calculate the amount of methacrylic anhydride to achieve
complete substitution.
We achieved transformation of the hydroxyl groups using methacrylic anhydride in the presence
of DMAP in 1,4-dioxane. The NMR spectra demonstrate that the degree of substitution we
achieved was almost 98%. We also note a relatively large peak associated with –COOH groups
(Figure 1, asterisk) and attributable to methacrylic acid (Scheme 1, red molecules) that we were
unable to rinse with successive sodium bicarbonate washes, which we have noted previously for
other organosolv lignins.21,22
We also confirmed the installation of methacrylate groups onto low-MW lignin using 1H-13C
HSQC NMR spectroscopy. The geminal vinylic protons associated with the installed C=C
moieties (which are not native to technical lignin) are clearly shown in Figure 2 below. We have
1
tentatively assigned these peaks by simulating a H-13C HSQC NMR spectrum of
permethacrylated vanillyl alcohol (molecule shown in Figure 2 inset) using software provided at
nmrdb.org.34–37
13
Figure 2. Experimental 1H-13C NMR spectrum of M-lignin showing signals associated with the
geminal protons of installed methacrylate moieties which are not native to technical lignin. Peak
assignments were made by simulating the spectrum of the permethacrylated vanillyl alcohol
molecule shown.
Stereolithography resin formulation and characterization
We blended M-lignin with a commercial clear SLA resin at different loading percentages. Given
the viscosity of the existing commercial resin, we employed a benchtop kinetic mixer to
accomplish this blending procedure. The powdery lignin sample smoothly blended with the
viscous resin after no more than 30 min stirring in the kinetic mixer. The resins appear as relatively
homogenous brown mixtures as shown in Figure 3 below.
14
Figure 3. Photograph of a representative sample of a lignin-commercial resin blend after mixing.
The sample appears to be a homogenous brown mixture with no apparent undissolved particles.
However, although the resins appear homogenous, we were interested in some quantitative
measures of their homogeneity. Resin viscosity is a crucial parameter in stereolithography. Resins
with low viscosity will flow easily during the printing process, which depends on a moving build
platform through the liquid resin bath. In contrast, resins with too high viscosity can affect printing
speed and resolution. Figure 4 summarizes the rheological properties of the lignin-containing
resins.
15
Figure 4. Flow curves (A) and viscosity curves (B) of the commercial base resin (gray squares)
and lignin-containing resins containing 1% (green), 2% (pink), 5% (orange), and 10% (blue) (w/w)
lignin. The insets (highlighted in green) depict the areas between 10-30 Hz, which is a shear range
common for many desktop SLA printers.38
At low shear rates, the base resin behaves as Newtonian fluid, given it is a mixture of relatively
small molecular weight materials. In addition, resins containing up to 5% (w/w) lignin also exhibit
Newtonian behavior, although their viscosity is higher overall due to the presence of lignin. Most
importantly, in the shear rate regime of 10-30 Hz (Figure 4 green shaded region), common for
desktop SLA printers,38 the Newtonian behavior of these resins combined with their viscosities
that do not exceed 5 Pa∙s (a common upper limit for SLA resin viscosity)25 leads us to conclude
these resins would be suitable for 3D printing by stereolithography.
In the case of the resin containing 10% (w/w) lignin, the resulting non-Newtonian colloidal
suspension behaves as a jammed “fragile matter” system.39 In a jammed system, at low shear rates,
an apparent yield stress must be overcome to initiate flow. Once this apparent yield stress is
16
overcome, the viscosity drops rapidly (shear thinning). However, at high shear rates, the viscosity
rises and potentially plateaus (shear thickening).40 This behavior is ubiquitous in colloidal
suspensions containing a high concentration of nonaggregating solid particles.41 These data imply
that at high concentrations, our M-lignin is perhaps not as uniformly dispersed as is apparent upon
visual inspection of the resins.
Even so, in the 10-30 Hz regime, the shear thinning behavior and acceptable viscosity of the
10% (w/w) suspension suggest the material is still printable. However, a common method to
shorten print times is to shorten lift and retract speeds of the printer, which are the speeds at which
the build platform moves away from and towards the bottom of the resin bath between layers,
respectively. If that speed is too fast, the shear rates experienced by the resin may exceed 30 Hz.
In this case, the shear thickening behavior of the resin might cause the lignin particles to flocculate,
which could create discontinuities in printed objects and detrimentally affect their performance
properties.
Next, we characterized the curing parameters of the resins. Although the curing parameters are
inherent to the liquid resins, measurement of a working curve that indicates penetration depth and
critical curing energy is accomplished by printing a windowpane object. These curves were
constructed as we have described previously, and the results of these measurements are
summarized in Figure 5 below.
17
Figure 5. Plots of penetration depth (A) and critical curing energy (B) versus lignin loading (color
scheme matches Figure 4). Each measurement was performed 3 times by printing 3 separate
windowpane specimens, and the means (markers and values) and standard errors of the mean (error
bars and parenthetical values) are shown. Values in parentheses are the standard error of the
preceding digit. In some cases, error bars are smaller than the size of the markers and are thus
obscured. Non-parametric statistical analysis (Kruskal-Wallis H test followed by Mann-Whitney
U test) was used to determine statistical differences among the samples (letters a-d); samples that
are not statistically different share letters. The dotted lines are not mathematically meaningful and
are provided to guide the eye.
The penetration depth of curing light in a photosensitive resin (such as those used for SLA 3D
printing) follows a Beer-Lambert relation and is defined as the depth at which the intensity of the
18
penetrating light falls to e-1 the intensity of the light at the surface of the resin.42 At a basic level,
it stands to reason that the penetration depth of a given resin will be lower if the material is darker.
This phenomenon is depicted in Figure 5a, whereby the measured penetration depth decreases with
additional brown lignin. Although the exact cause for this phenomenon is still unknown, we posit
that the electronic response of the resin material (governed by the sum of the electronic structures
of all the components) changes substantially upon addition of lignin. Since lignin contains
delocalized π-electrons that give rise to its light absorptive properties (i.e., lignin is brown43),
changes in reflectance and absorption in the resin due to lignin’s electronic structure necessarily
reduce the penetration depth of curing light.44
Results related to the critical curing energy displayed in Figure 5b are somewhat surprising.
Critical curing energy corresponds to the minimum energy required to activate the photoinitiator
and initiate the polymerization reaction. One might expect an inverse relationship, that as
penetration depth decreases, critical curing energy should increase: fewer photons find
photoinitiator molecules deep within the resin, and therefore more overall are required to initiate
a polymerization reaction. However, as shown in Figure 5b, as the amount of lignin increases, the
critical curing energy decreases, in fact by 2-3 orders of magnitude depending on the amount of
lignin used.
This result surprised us, but we have developed a tentative explanation. Technical Kraft lignin
contains several aromatic moieties that are conjugated with aliphatic ketones, which is a result of
oxidizing conditions during the pulping process that convert aliphatic –OH groups to ketones (or
aldehydes or carboxylic acids). As such, lignin can act as a Norrish Type-II photoinitiator, which
is a class of molecules known to absorb in the near-UV-to-visible range (our 3D printer emits at
405 nm) and form energetic species that can abstract protons from neighboring molecules to form
19
radicals and initiate photopolymerizations.45 While our acetylation method converts nearly all the
free –OH groups in lignin to methacrylate esters, there are some phenolic –OH groups that remain
even after conversion (see Figure 1b above). Under the right conditions, these could be converted
to quinones during photoinitiation, which are chemical species known to be Norrish Type-II
photoinitiators.46–48 In effect, the lignin is acting as additional photoinitiator, thereby aiding in the
polymerization reaction. This is an exciting result, as if it could be controlled, lignin could be used
to alter the light absorption properties of 3D printer resins by controlling its electronic structure
via chemical modifications. These investigations are ongoing in our laboratory.
Printed objects and mechanical testing
With lignin-containing resins in hand, we were interested in probing what effect the modified
lignin had on the mechanical properties of printed objects. We printed tensile testing specimens
using a desktop SLA printer and subjected the resulting specimens to static tensile testing to
measure tensile strength, elongation, and Young’s modulus. The results of these measurements are
summarized in Figure 6 below.
20
Figure 6. Plots of ultimate tensile strength (A), strain at break (B), and Young’s modulus (C) of
printed objects versus lignin loading (color scheme matches Figures 4 and 5). Each measurement
was performed at least 4 times by printing separate tensile testing specimens. Types of information
displayed and statistical analyses are identical to Figure 5.
The tensile tests we performed indicate that the tensile strength of the commercial resin
decreases upon addition of lignin, with a statistically significant decrease of 37% upon addition of
5% (w/w) lignin, and a decrease of nearly 57% upon addition of 10% (w/w) lignin (Figure 6a).
We attribute this to the relatively low molecular weight of the lignin added. As the percentage of
low molecular weight material increases as a function of the total mixture, the intermolecular
21
interactions between chains become less pronounced, thereby leading to an overall decrease in
strength.
Furthermore, the strain at break of the commercial resin decreases upon addition of lignin, with
a statistically significant 74% decrease in strain at break for the sample containing 10% (w/w)
lignin (Figure 6b). In general, highly crosslinked photopolymers are relatively brittle. Since the
lignin oligomers we add could each be multifunctional (each having multiple –OH groups
acetylated with methacrylic esters), addition of lignin would substantially increase the crosslink
density of the resulting printed objects. In that case, the objects would become much more brittle
as depicted in Figure 6.
Moreover, we noted an overall decrease in Young’s modulus upon addition of lignin, with a
statistically significant decrease of 13% for the sample containing 10% (w/w) lignin (Figure 6c).
We attribute this decrease in flexibility to the crosslinking phenomenon described above. As
crosslink density increases with lignin content, polymer chains are less able to slide past one
another in the printed object, and the overall flexibility of the object is diminished.
CONCLUSIONS
We have reported on a method to create Kraft-lignin-containing stereolithography resins that
can be 3D printed using a desktop 3D printer. Fractionation of Kraft lignin using acetone afforded
a low-MW fraction that we were able to acetylate with methacrylate ester groups nearly
quantitatively. This low-MW, highly substituted material allowed us to create new resins from
commercial SLA resins with ten times the amount of Kraft lignin previously reported. The resins
were relatively homogenous, except at the highest lignin loading, and we were able to successfully
print tensile testing specimens. Working curve measurements suggest that the lignin participates
in the photopolymerization process, perhaps by absorbing light and generating active species that
22
can then react to form radicals for polymerization. However, although we chose to incorporate
fractionated low-MW lignin to enhance its overall solubility in the resin materials, these low-MW
oligomers likely contribute to a decrease in strength to the printed objects. We were able to include
a much larger overall percentage of Kraft lignin in our samples than previously reported, but at the
expense of the tensile strength of the printed objects. In addition, our acetylation method to add
methacrylate esters to lignin probably enhanced its interactions with the resulting photopolymer
through covalent interactions. However, the increase in crosslink density imparted by addition of
multifunctional lignin oligomers increased the brittleness of the objects and decreased their
flexibility. These results are simultaneously promising and frustrating and they highlight the need
to further our fundamental understanding of how lignin behaves in photopolymer resins. These
investigations are ongoing in our laboratory.
23
Corresponding Author
* E-mail: sc411@psu.edu
ORCID
Stephen C. Chmely: 0000-0002-2637-9974
Author Contributions
The manuscript was written through contributions of all authors. SCC conceived and designed
the experiments, obtained funding, interpreted data, and wrote the manuscript. WSL collected
rheology data for the resins. GPM collected GPC data for the lignin samples. MRG and AA
collected data related to 3D printing and all performed the remaining characterizations. All
authors have edited and given approval to the final version of the manuscript.
Funding Sources
This work was supported by funding from the United States Department of Agriculture USDA-
NIFA Project PEN04671 and Accession number 1017582. SCC and MRG also acknowledge
support from USDA-NIFA under grant number: 2020-68012-31881. The findings and conclusions
in publication have not been formally disseminated by the United States Department of Agriculture
and should not be construed to represent any agency determination or policy.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
The authors wish to acknowledge the Penn State Materials Characterization Lab for use of the
Bruker Vertix 70 FTIR spectrometer. We also wish to acknowledge the support of Dr. Christy
24
George and Dr. Tapas Mal for their help with collecting NMR data, and the support of Jerry
Magraw for his help with collecting GPC data.
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Methacrylated Kraft Lignin As A Double Edged Sword A Quantitative Analysis of Kraft Lignin Containing Objects Printed by Stereolithography

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Methacrylated Kraft Lignin As A Double Edged Sword A Quantitative Analysis of Kraft Lignin Containing Objects Printed by Stereolithography

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Methacrylated Kraft lignin as a double-edged sword:

a quantitative analysis of Kraft lignin-containing

objects printed by stereolithography

University Park, PA 16802 USA

KEYWORDS Kraft, lignin, 3D printing, stereolithography, additive manufacturing

ABSTRACT Finding an alternative to fossil-based resins which is renewable, sustainable, and

affordable is an important step to enable large-scale industrial manufacturing using

commercially available stereolithography resin produce 3D printed objects. We thoroughly

industrially relevant lignin.

Additive manufacturing by 3D printing is an effective and innovative way to fabricate materials

compared to conventional manufacturing processes. It allows users to efficiently produce materials

focused on developing new photoactive resins with interesting combinations of properties.3

for industrial 3D printing.7

precursors.5,15 Investigations focused on using lignin in multicomponent resins for 3D printing by

printing technologies.16 Some examples of well-characterized resins containing phenolic

tremendous amount of research.20

Instead, incorporation of technical lignin, such as Kraft or organosolv, is emerging as a method

performance properties because of the lignin present.

resins are mixed.

objects 3D printed from resins that contain it.

behavior and present some potential solutions below.

MATERIALS AND METHODS

It was fully characterized as described below. SainSmart Rapid UV General Purpose

(MilliporeSigma, Burlington, MA USA), chloroform-d, and dimethyl sulfoxide-d6 (Cambridge

Lignin fractionation and preparation

followed by drying under vacuum at ambient temperature for 24 h.

subsequent experiments unless otherwise noted.

following a procedure described elsewhere.28

performed as described elsewhere.29

calculated by referencing to the clean bare crystal.

friable powder using a mortar and pestle.

Resin formulation and characterization

to protect them from light prior to printing.

Rheological properties of the formulated resins were measured using a TA Instruments

3D printing and mechanical testing

measured and reported as an average of at least 4 replications.

number of samples collected, a non-parametric Kruskal-Wallis one-way analysis of variance was

hoc Mann-Whitney U test (95% confidence level) of the null hypothesis.31

RESULTS AND DISCUSSION

Lignin preparation, modification, and characterization

Table 1. Molecular weight distributions of parent Kraft and fractionated lignins.

Sample Mn (g/mol) Mw (g/mol) Ð

Kraft lignin 2684 3257 1.213

High-MW lignin 2717 3313 1.219

Low-MW lignin 1959 2135 1.09

MW lignin.32 We hypothesized that this enhanced solubility would be beneficial regarding

Accordingly, we modified this low-MW lignin using methacrylic anhydride as demonstrated in

Scheme 1. Modification of softwood Kraft (primarily guaiacyl-type) lignin with methacrylic

other organosolv lignins.21,22

Stereolithography resin formulation and characterization

homogenous brown mixtures as shown in Figure 3 below.

measures of their homogeneity. Resin viscosity is a crucial parameter in stereolithography. Resins

common for many desktop SLA printers.38

these resins would be suitable for 3D printing by stereolithography.

visual inspection of the resins.

summarized in Figure 5 below.

obscured. Non-parametric statistical analysis (Kruskal-Wallis H test followed by Mann-Whitney

are provided to guide the eye.

reduce the penetration depth of curing light.44

via chemical modifications. These investigations are ongoing in our laboratory.

Printed objects and mechanical testing

summarized in Figure 6 below.