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Cellular, Mineralized, and Programmable Cellulose
Composites Fabricated by 3D Printing of Aqueous Pastes
Derived from Paper Wastes and Microfibrillated Cellulose
Benjamin Stolz and Rolf Mülhaupt*
Combining recycling of paper wastes (WPs) with extrusion-based additive
manufacturing represents a sustainable route to cellular cellulose composites
tailored for lightweight construction. Particularly, shear mixing of shredded
WPs with an aqueous solution of a polymer binder like polyvinyl alcohol
(PVA) yields aqueous pastes suitable for 3D printing. As a shear thinning
additive, both WP and microfibrillated cellulose account for enhanced shear
thinning and dimensional stability. Opposite to the formation of dense WP/
PVA composites by melt extrusion, 3D printing of aqueous pastes produces
cellular cellulose/PVA composites exhibiting hierarchical pore architectures.
In spite of low densities around 0.8 g cm−3, high Young’s modulus (2.0 GPa)
and tensile strength (53 MPa) are achieved. Mechanical stability, water resist-
ance, and even flame retardancy simultaneously improve by crosslinking with
glyoxal and especially by mineralization. Multimaterial 3D printing combines
the 3D dispensing of cellulose/PVA pastes with the simultaneous, staged,
or subsequent spraying of aqueous water glass to enable mineralization of
composite surface, bulk, and interlayers. Furthermore, the glyoxal-mediated
crosslinking affords thermo- and moisture-responsive cellulose/PVA compos-
ites with programmable shape change induced either by heating at 100 °C or
by exposure to moisture at 37 °C.
1. Introduction
Today growing public concerns with respect to global warming
and the rapid depletion of fossil resources is stimulating the
development of materials derived from renewable resources.[1]
Traditionally, in addition to exploiting biopolymers like natural
B. Stolz, Prof. R. Mülhaupt
Freiburg Materials Research Center (FMF) and Institute for
Macromolecular Chemistry
University of Freiburg
Stefan-Meier-Strasse 31, 79104 Freiburg, Germany
E-mail: rolfmuelhaupt@web.de
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/mame.201900740.
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim. This is an open access article under the terms of the Creative
Commons Attribution-NonCommercial License, which permits use, dis-
tribution and reproduction in any medium, provided the original work is
properly cited and is not used for commercial purposes.
The copyright line for this article was changed on 24 March 2021 after
original online publication.
DOI: 10.1002/mame.201900740
Macromol. Mater. Eng. 2020, 305, 1900740 1900740  (1 of 12) © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
rubbers, a great variety of plant fibers and
bio-based fillers like wood flour are com-
pounded with synthetic thermoplastics and
thermosets.[2–4] Most of these wood plastic
compounds are being processed by forma-
tive processing like injection molding,
extrusion, blow molding, and casting, all
of which require the use of molds. Since
the 1980’s the solid free-form fabrication,
referred to as additive manufacturing
(AM) and 3D printing, has emerged as
highly versatile digitalized processing
technology in which digitally sliced com-
puter-designed objects are directly trans-
lated into the layer-by-layer assembly of
objects in the absence of molds.[5] During
the pioneering days 3D printing technolo-
gies like stereolithography have served
the specialized needs of niche markets
like rapid prototyping.[6,7] However, at the
beginning of the 21st century, the scope
of additive manufacturing is broadening
with respect to both the commercially
available 3D printing technologies and
their applications. Nowadays, apart from
vat photopolymerization, AM includes
powder bed fusion, binder jetting, sheet lamination, and extru-
sion-based 3D printing, which is highly robust and enables
processing of an extraordinarily wide spectrum of organic and
inorganic materials.[5] Extrusion-based AM can be divided into
two different categories: fused filament fabrication (FFF), also
named fused deposition modeling (FDM), and 3D dispensing.
In the FFF process, pioneered in 1989, filaments of thermoplas-
tics are fed into a heated nozzle in which the polymer melts, is
extruded and 3D deposited on a built plate where it solidifies
by means of glass transition or crystallization, respectively, after
cooling.[8] In contrast, extrusion-based AM by 3D dispensing
resembles hotmelt dispensing and had been established in 2000
for 3D printing of synthetic and natural polymers including 3D
printing of melts, pastes, solutions, and dispersions.[9] In this
3D dispensing process, thermoplastics, thermosets, elastomer
prepolymers, as well as synthetic and biopolymers, metal and
ceramic pastes, cement, polymer solutions, and polymer disper-
sions are 3D printed by pneumatic 3D dispensing without using
valves. Going well beyond the physical solidification typical for
FFF of thermoplastics also chemical solidification by means of
ionomer formation, crosslinking, and other chemical reactions
including enzyme catalysis are feasible. Moreover, no temporary
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support structures are required in the so called zero-gravity 3D
dispensing in which 3D printing takes place in a liquid media
by carefully matching the density of the 3D printed material
and the liquid printing medium.[5] Particularly in view of appli-
cations in regenerative medicine, the 3D dispensing process is
highly attractive and has emerged as the technological base of
3D bioprinting, also named bioplotting.[10,11] For example, cell-
laden sodium alginate solutions can be printed into solutions
of CaCl2 in order to obtain crosslinked and solidified bioactive
hydrogels for tissue engineering.[5,12–14] This exceptionally broad
variety with respect to materials choice and application range
is impressively reflected by the development of mega scale 3D
printers in the construction industry. In the so called contour
crafting process, cement dispersions are 3D printed in the
meter scale to build entire houses at low cost within less than
one day while reducing energy consumption and wastes with
respect to conventional cement processing.[15,16]
Since cement production is associated with massive emission
of the greenhouse gas carbon dioxide, several attempts have been
made to exploit renewable materials in lightweight construction.
Among polymers derived from renewable resources, cellulose
is the most abundant polymer and cellulose composites of both
natural and synthetic polymers are well known for many dec-
ades. For instance, wood plastic compounds (WPCs) based on
polypropylene (PP) are employed in automotive, packaging, fur-
niture, and construction industries due to their good mechanical
properties such as high Young’s modulus and tensile strength at
low weight.[17,18] Today, WPC filaments are commercially avail-
able for FFF processes in which the mechanical properties are
governed by the wood content.[19] In another approach, Li et al.
employed cellulose solutions in N-methylmorpholine-N-oxide in
3D dispensing and subsequent solvent removal with water and
freeze drying to fabricate complex cellulose structures containing
ordered interconnected pores.[20] Apart from conventional cellu-
lose-based composites, 3D printing of materials containing nano-
cellulose is intensively investigated.[10] During the last decade,
progress has been made with respect to the isolation, characteri-
zation, and application of micrometer- and nanometer-sized cel-
lulose like cellulose nanocrystals (CNCs), also named nanocrys-
talline cellulose (NCC), microfibrillated cellulose (MFC) also
referred to as nanofibrillated cellulose (NFC) or cellulose nanofi-
brils (CNFs), respectively, and enzymatically fabricated bacterial
nanocellulose (BNC).[21] During the recent five years, nanocel-
lulose containing filaments based on poly(lactide acid) (PLA),
poly(ε-caprolactone), and poly(vinyl alcohol) (PVA) have success-
fully been developed for 3D printing by FFF.[10,22] Opposite to
FFF, 3D printing by means of 3D dispensing does not require fil-
aments and employs aqueous pastes. Frequently drying and melt
compounding of nano- and micro­meter-sized cellulose with poly-
mers are accompanied by massive agglomeration and dispersion
problems due to the strong intermolecular hydrogen bridges. In
contrast, 3D dispensing of aqueous cellulose-based pastes is a
facile way to meet the physical requirements of the printing ink
accompanied by the retention of sub-micro-sized cellulose fibril
morphology. For example, in case of MFC, the nanocellulose is
obtained as an aqueous suspension after delamination of pulp
under high shearing and varying preprocessing steps such as
2,2,6,6-tetramethylpiperidinyloxyl (TEMPO)-mediated oxidation
or enzymatic pretreatment of the pulp, respectively.[21,23,24] Thus,
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cellulose-based inks for 3D dispensing are readily available when
using aqueous MFC dispersions without requiring an interme-
diate drying and redispersion. During recent years, nanocellulose
was exploited for tissue engineering and wound dressing applica-
tions using 3D dispensing by adding sodium alginate to the sus-
pension and subsequent crosslinking by CaCl2 addition.[14,25–29]
Furthermore, CNC dispersed in either water or a photopolym-
erizable mono­mer was employed in 3D printing of cellular cel-
lulose architectures exhibiting tailored mechanical property
profiles.[30] In a recent advance, pulp fibers were obtained
from bagasse by soda and hydrothermal treatment followed by
TEMPO-mediated oxidation to yield CNF inks for 3D printing.[31]
Alternatively, enzymatic nanocellulose was obtained from a pine
sawdust pulp.[32] It is well recognized that 3D printing holds
great prospects for forest products ranging from wood fibers to
wood-based biomaterials, especially with respect to the sustain-
able development of materials for lightweight construction and
architecture.[33–35] Attempts have been made to exploit wastes
like reclaimed and discarded materials containing plant fibers as
raw material for 3D printing using enzyme-catalyzed deinking to
improve plant fiber whiteness.[36]
While conventional 3D printing fabricates objects that retain
the same shape and mechanical properties during their entire
product lifetime, 4D printing introduces time as the fourth
dimension to produce programmable and smart materials,
which respond with property changes to external stimuli.[5,37–39]
For instance, as a function of the print design and the mate-
rial choice in multimaterial printing, programmed shape
changes can be triggered either by heat, light, electricity, or
moisture.[37,39–42] According to Chen et al., PVA, crosslinked by
hydrogen bonding or by covalent bonds between PVA and the
diisocyanate crosslinker, respectively, exhibits shape memory
behavior, which can be triggered either by heating at tempera-
tures above glass transition temperature (Tg) or by water immer-
sion, respectively.[43] This concept has not been transferred to
the field of 3D printing yet. During recent years, 4D printing
of hydrogels for applications in tissue engineering has been
developed to enable programmable and stimuli-responsive
shape changes of 3D printed material systems.[44,45] Moreover,
Menges and co-workers have developed 4D printing processes
and materials with moisture-induced shape change for appli-
cations in architecture mimicking plant structures like leaves
and cone scales.[46–48] To the best of our knowledge, no reports
have appeared in literature yet concerning 3D/4D printed shape
memory materials fabricated by 3D dispensing of cellulose/
PVA composites and subsequent crosslinking.
Since the rapid growth of human population on our planet is
accompanied by an increasing demand of energy and resources,
the exploitation of renewable feedstocks for 3D printing repre-
sents an important challenge. Particularly, paper wastes (WPs)
represent an abundant source of bio-based raw materials unex-
ploited in 3D printing. WP recycling is well established in paper
industry and has a high demand of chemicals like surfactants,
hypochlorite, ozone, oxygen, or peroxides used for deinking.[49,50]
Several strategies have been established to use cellulose fibrils
derived from paper wastes as reinforcing filler in WPCs.[51–56]
For example, López et al. reported on injection-molded PP/WP
composites containing 50 wt% waste paper and exhibiting a ten-
sile strength of 56 MPa and a Young’s Modulus of 7.4 GPa.[52]
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Figure 1.  The synthetic route to aqueous WP/PVA pastes and composites prepared by combining paper recycling with 3D printing; shredding a news-
paper (step A) is followed by shear-induced blending with water in the presence of PVA (step B) to produce aqueous WP/PVA pastes for extrusion-based
3D printing of honeycomb-like architectures (step C).
Frequently, oxidation and purification by flotation processing
are required to remove WP impurities like printing ink, binders,
and coatings. It is obvious that such WP pretreatment adversely
affect the ecological and economic benefits related to using WP
as sustainable material. Herein, we report on combining paper
recycling with 3D printing in which untreated WP serves as the
raw material for the 3D dispensing of aqueous cellulose pastes
and the formation of honeycomb-like cellulose composites with
hierarchical pore architectures. The 3D printing of aqueous
WP and MFC pastes also targets the fabrication of cellulose/
polyvinyl alcohol composites, which are crosslinked with gly-
oxal to afford programmable materials with temperature- and
moisture-induced shape change. In multimaterials 3D printing,
the 3D dispensing of aqueous WP pastes is combined with 3D
dispensing of water glass (WG) by spraying to prevent the need
of WP pretreatments and to examine the impact of mineraliza-
tion on mechanical properties, water resistance, and flame retar-
dancy of cellular cellulose/PVA composites.
2. Results and Discussion
2.1. Printing of Cellular Cellulose Composites
WP is shredded (Figure  1, step A) and then blended together
with water in a shear mixer (Figure 1, step B) to obtain aqueous
WP slurries. There are two ways to obtain WP/PVA pastes,
which are readily tailored to meet the requirements of 3D
printing (Figure 1, step C): Either freeze-dried WP derived from
the slurries is added to an aqueous PVA solution or the PVA
Figure 2.  SEM images of a) dried WP and b) commercial MFC (WMFCQ_standard, 100× diluted 3.5 wt% aqueous dispersion supplied by Weidmann
Fiber Technology).
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is added directly to the aqueous WP slurries. In bench scale,
a simple hand-held kitchen blender produced WP/PVA pastes
from shredded newspaper to meet the demands of extrusion-
based 3D printing. Neither special deinking processes nor other
pretreatments were required. After drying by freeze drying,
the morphology of WP was determined by means of scanning
electron microscopy (SEM; Figure  2). Herein, WP exhibits a
heterogeneous fiber-like morphology with fiber dimensions
which are about two orders of magnitude higher than those of
commercial MFC (WMFCQ_standard, 3.5 wt% aq. dispersion
supplied by Weidmann Fiber Technology). Obviously, aqueous
WP/PVA pastes derived directly from WP slurries in water rep-
resent low cost and environmentally friendly route to easy-to-
disperse short and long WP fibers with diameters up to 10 µm
and length up to the millimeter scale.
For extrusion-based 3D printing, shear thinning is the prime
requirement to enable processing of pastes, which must have
low viscosity at high shear but immediately solidify at zero
shear after passing through the nozzle of the print head. The
addition of either WP or MFC, respectively, was essential for
adjusting the cellulose/PVA paste viscosity by shear thinning
during 3D printing. Moreover, the presence of WP was the key
to assure the long-term structural integrity of the 3D printed
objects whereas aqueous PVA in the absence of cellulose did
not meet the demands of 3D printing. Figure 3 displays the fre-
quency sweeps using a plate-to-plate rheometer at a constant
strain amplitude of 1%. The strain of 1% was chosen to identify
the influence of the WP content on the shear thinning effect.
It should be noted that the applied strain and shear rates do
not correspond to the optimized parameters of the 3D printing
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Figure 3.  Left: SEM image of A) 3D printed WP12/PVA and B) PVA of
hexagonal structures. Right: viscosity of aqueous PVA solutions (20 wt%)
containing 0 wt% WP (PVA), 12 wt% WP (WP12/PVA), 20 wt% WP
(WP20/PVA), 28 wt% WP (WP28/PVA), and 15 wt% MFC (MFC15/PVA).
The viscosities as determined via frequency sweeps using a plate-to-plate
rheometer at a constant strain of 1%.
process but enable a preliminary ranking and selection of the
shear thinning additives. As is apparent from Figure 3, the
viscosity of an aqueous PVA solution containing 20 wt% PVA
(weight average molar mass of 185 000 g mol−1 and degree of
polyvinylacetate hydrolysis of around 88%) was too low and
the printed honeycomb structures disintegrated due to mas-
sive flow occurring immediately after completing 3D printing.
By adding up to 28 wt% WP, as referred to the total WP+PVA
solids content, the rheological properties of WP/PVA pastes
meet the requirements of 3D printing since the viscosity of
the paste increased with increasing WP content but exhibited
significant shear thinning. Most likely the shear thinning of
WP/PVA and MFC/PVA pastes is attributed to the presence of
hydrogen bondings between the hydroxyl groups of the cellu-
losic materials. The sample code denotes the type of the cel-
lulosic material (WP or MFC) together with its content in the
aqueous cellulose/PVA mixture. At a WP content exceeding
12 wt% the resulting WP12/PVA pastes enabled to print stable
honeycomb structures. Due to their lower average fiber diam-
eter (Figure 2), smaller amounts of MFC (15 wt%) accounted
for similar shear thinning and increase in viscosity with respect
to WP20/PVA containing a higher amount of 20 wt% WP.
Dimensionally stable honeycomb structures as well as ten-
sile test bars were 3D printed by means of 3D dispensing using
aqueous WP20/PVA and MFC15/PVA pastes (Figure  4). Typi-
cally, dispensing nozzles with a diameter of 0.41 mm were used
and 3D dispensing was performed by means of the 3D Biop-
lotter from EnvisionTEC at a maximum air pressure of 5.0 bar.
Typically WP20/PVA pastes containing 20 wt% WP20 were
used to examine the structure/property correlations, since at
the tolerated maximum of 28 wt% WP, occasional clogging of
the nozzle was encountered. After completing the 3D printing
of cellulose/PVA composites, the dimensions of the obtained
3D printed structures exhibited a deviation of around 10% with
respect to the specifications of the CAD model. Typically the
printed cellulose/PVA composites were dried for two weeks
under a continuous air flow at room temperature. This drying
process was accompanied by a significant vertical shrinkage
due to water evaporation. In case of the 3D printed tensile test
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Figure 4.  3D dispensing of a) WP20/PVA and b) MFC15/PVA to fabricate
dimensionally stable honeycomb structures using the Bioplotter from
EnvisionTEC.
bars, the vertical shrinkage ranged from 53 ± 2% for WP12/
PVA to 60 ± 7% for WP28/PVA as compared to the height of
the printed specimens in the wet state immediately after com-
pleting 3D printing prior drying. Furthermore, two different
post-treatments by crosslinking or mineralization, respectively,
were examined to improve both the water resistance and the
mechanical properties of the printed structures. Crosslinking
of cellulose/PVA composites was achieved by immersing the
3D printed objects in an aqueous 40 wt% glyoxal solution.
Alternatively, cellulose/PVA composites were mineralized by
exposing them to an aqueous water glass solution. After com-
pleting the post–treatments, the resulting samples were dried
at room temperature. All post-treatments markedly reduced the
vertical shrinkage ranging from 38 ± 3% for glyoxal crosslinked
samples to 46 ± 7% for water glass treatment. Regardless of
the post-treatment cellular cellulose/PVA composites with
similar pore structures were formed. According to SEM and
micro X-ray computer tomography (μ-CT) images displayed
in Figure  5, all WP20/PVA composites contained micrometer-
sized closed pores with average diameters ranging between 50
and 200 µm. Since 3D printing also allowed to design much
larger pores in millimeter and centimeter range via varying
the 3D printing pathways, the resulting honeycomb structures
exhibited hierarchical pore architectures combining microm-
eter-sized pores with millimeter- and centimeter-sized pores.
This formation of hierarchical pore structures is not achieved
by conventional melt processing. When WP20/PVA was
immersed in an aqueous WG solution, a dense silicate layer
was formed at the WP20/PVA_WG surface, whereas the pores
inside were unaffected and identical with those of untreated
WP20/PVA after drying in air. It is well known that water glass
reacts with cellulose and cellulose-based materials to form sili-
cate/cellulose composites, which exhibit significantly improved
water and flame resistance.[57,58] Obviously, this silicate surface
coating acted as barrier layer preventing water glass infiltration
of the WP/PVA composites. Thus, the pores remained intact
and were unaffected by water glass addition. While only dried
WP20/PVA and WP20/PVA_WG were robust enough to enable
mechanical handling, the glyoxal (Gly) crosslinked composite
WP20/PVA_Gly was mechanically stable also in its wet state
immediately after completing its immersion in aqueous gly-
oxal solution (40 wt%) for the duration of 3 days. This behavior
is attributed to the successful crosslinking of bulk WP20/
PVA_Gly whereas in WP20/PVA_WG only the surface was
crosslinked by mineralization. As compared to the untreated
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Figure 5.  SEM images of a) WP20/PVA and b) WP20/PVA_WG that was immersed in an aqueous water glass solution and contains a dense silicate layer
at the surface whereas the pores in bulk remained intact; c) µ-CT image of cellular WP20/PVA_Gly prepared by crosslinking of WP20/PVA with glyoxal.

WP20/PVA, dynamic scanning calorimetry (DSC) measure-
ments revealed the disappearance of the PVA melting tempera-
ture by crosslinking with glyoxal. Moreover, crosslinking with
glyoxal rendered PVA water insoluble. This presents additional
experimental evidence for the successful PVA crosslinking by
means of the glyoxal addition. Similar to untreated WP20/
PVA and WP20/PVA_WG mineralized with water glass, the
crosslinked WP20/PVA_Gly samples exhibited high porosity as
verified by means of µ-CT imaging displayed in Figure 5c.
As a proof of concept, a layer of WP20/PVA or MFC15/
PVA, respectively, was 3D printed followed by spraying a
40% aqueous water glass solution by means of a hand-held
dispenser. This procedure was repeated two times aiming at
creating three-layer cellulose/PVA composites having a sand-
wich-type architecture in which a silicate layer is embedded
between two cellulose/PVA layers. The SEM images of the
cross-section of the corresponding 3D printed tensile test
specimens are displayed in Figure  7. No multilayer struc-
ture with strictly alternating layers are visible but Figure 7a,b

2.2. Mineralized Cellulose Composites

Since post-treatment of WP/PVA composites with water glass

exclusively mineralized the composite surface (Figure 5b), in
multimaterials 3D printing, the 3D extrusion of WP/PVA pastes
was combined with spraying of aqueous water glass solutions.
In principle, there exist three different modes for multimate-
rials 3D printing. In the first mode, the water glass solution is
sprayed on top of the printed WP/PVA composites to miner-
alize the surface and to form a silicate coating, thus eliminating
the time-consuming post-treatment by immersing the printed
composites for a prolonged period of time in a water glass solu-
tion. In the second mode, the 3D printing of WP/PVA pastes
alternates with the spraying of the water glass solution to build
Figure 6.  a) Multimaterials 3D printing of cellulose/PVA pastes together
multilayer composites containing alternating silicate and WP/
with the simultaneous or staged spraying of the aqueous water glass solu-
PVA layers. In the third mode, the simultaneous 3D dispensing tion to form b) cellular cellulose/PVA composites containing a silicate
of both WP/PVA and aqueous water glass solutions forms uni- surface coating, c) cellular multilayer cellulose/silicate composites, or d)
formly mineralized WP/PVA composites (Figure 6). bulk-mineralized cellular cellulose/PVA composites, respectively.

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Figure 7.  SEM images of mineralized WP20/PVA composites prepared by multimaterial 3D printing in which the aqueous water glass solution was
sprayed during 3D dispensing of aqueous WP20/PVA pastes (WP20/PVA_WGsp); a) overview of porous structure; no separate silicate and WP/PVA
layers are detectable; b) a dense silicate layer is formed at the surface; c) at higher magnification, interfaces of WP/PVA and silicates are visible inside
the bulk material providing an evidence for the successful bulk mineralization.

reveals the formation of a dense silicate layer similar to that respect to that of melt-extruded cellulose/PVA composites.[59]
of a cellular composite prepared by post-treatment with As is apparent from Figure  8 the densities, as measured by
water glass (Figure 5b). Most likely, albeit sprayed in the means of pycnometry at 25 °C, of the neat WP20/PVA and
staged mode, the mineralization was too slow and allowed MFC15/PVA composites varied between 0.76 and 0.82 g cm−3
the migration of the water glass solution into the WP/PVA and were very similar to that of 3D printed PVA solutions
layers. When water glass was sprayed onto the 3D objects to
complete multimaterials 3D printing, a dense silicate surface
layer was formed similar to that of the composites post-treated
by immersing them in the aqueous water glass solution.
According to Figure 7c bulk mineralization is evident from
the formation of the interface at which a dense silicate phase
is allocated next to the rough WP/PVA phase containing WP
fibers. To achieve multilayer composite formation, the min-
eralization rate should be enhanced to prevent migration.
Nevertheless, this multimaterial 3D printing process enables
the formation of silicate coatings without requiring time-
consuming post-treatments. Moreover, it enables facile bulk
mineralization, which is not feasible by post-treatment. Bulk
mineralization with adversely affecting the pore architectures
is advantageous with respect to improving mechanical proper-
ties, water resistance and, even flame retardancy.

2.3. Density and Mechanical Properties

Figure 8.  Densities of PVA, WP20/PVA, and MFC15/PVA prepared by
The high porosity of the 3D printed cellular cellulose/PVA extrusion-based 3D printing as compared to the densities of cellulose
composites is reflected by significantly reduced density with and melt-extruded PVA.[59]

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Table 1.  Mechanical properties of 3D printed cellular WP/PVA composites as compared to 3D printed neat PVA in the absence post-treatment.
Composition WP content [wt%] Young’s modulus [MPa]
PVA 0 570 ± 90
WP12/PVA 12 610 ± 60
(+7%)
WP20/PVA 20 1120 ± 130
(+96%)
WP28/PVA 28 1990 ± 150
(+249%)
a)The
vertical shrinkage was determined by measuring the height of the dried specimens as compared to the height of specimens in wet state obtained immediately after
completing printing prior to drying.
but substantially lower with respect to melt extruded PVA
and cellulose. Yet the density of cellulose/PVA markedly
increased by post-treatment. Samples crosslinked with gly-
oxal showed the highest densities which accounted for a
mass increase resulting from glyoxal incorporation. In case
of WP20/PVA_Gly and MFC15/PVA_Gly the density was
comparable to melt-extruded PVA (1.28 g cm−3). The densi-
ties of cellulose/PVA composites mineralized with water
glass ranged between the densities of glyoxal-crosslinked and
untreated cellulose/PVA composites. The densities of both
WP20/PVA and MFC15/PVA achieved by staged multimate-
rial printing (sample code WGsp) were higher as compared
to those resulting from water glass post-treatment (sample
code WG). This is attributed to the higher water glass content
feasible by means of multimaterials printing with respect to
the post-treatment with water glass, which forms an imper-
meable silicate coating which restricts the WG uptake.
The mechanical properties of 3D printed type 5A test spec-
imen of cellular WP/PVA composites were evaluated by ten-
sile testing. First, the influence of WP addition on the prop-
erties of WP/PVA composites was elucidated as compared to
PVA processed under identical conditions by extrusion-based
3D printing of aqueous 20 wt% PVA solutions. Second, the
influence of post-treatments and the series of MFC/PVA
composites were evaluated and compared with multimate-
rials printing in the presence of water glass. The results con-
Figure 9.  Young’s modulus and tensile strength of 3D printed cellular WP/PVA composites as a function of the WP content as compared to PVA 3D
printed under identical conditions in the absence of WP and without applying a post-treatment.
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Tensile strength [MPa] Elongation at break [%] Vertical shrinkagea) [%]
17 ± 3 33 ± 12 66 ± 4
20 ± 2 5.7 ± 0.7 53 ± 2
(+18%)
30 ± 3 3.3 ± 0.5 56 ± 1
(+76%)
53 ± 3 4.4 ± 0.7 60 ± 7
(+212%)
cerning the influence of WP addition on the mechanical prop-
erties of cellular WP/PVA composites in the absence of post-
treatments are listed in Table  1 and Figure  9. Stiffness and
strength significantly improved with increasing WP content at
the expense of elongation at break. At the maximum WP con-
tent of 28 wt%, the Young’s modulus of WP28/PVA increased
to about 2 GPa (+250% with respect to neat PVA), while the
tensile strength tripled to reach 53 MPa.
The results of the tensile testing of WP20/PVA and
MFC15/PVA composites prepared by post-treatment and
by multimaterial 3D printing are presented in Table  2 and
Figure  10. Crosslinking as well as mineralization rendered
all cellulose/PVA compositions brittle. In fact, the MFC15/
PVA_Gly sample was too brittle for tensile testing. While
crosslinking of WP20/PVA with glyoxal did not affect Young’s
modulus and tensile strength, both post-treatment and mul-
timaterial 3D printing with water glass afforded significant
improvements of the mechanical properties. As compared
to post-treatment the multimaterial 3D printing, in which
water glass was sprayed in between extruded cellulose/PVA
layers, accounted for markedly higher stiffness and ten-
sile strength. The best results with respect to stiffness and
strength were observed for cellular MFC15/PVA_WGsp com-
posites exhibiting a Young’s modulus of 2.4 GPa and ten-
sile strength of 50 MPa despite of its high porosity and low
density.
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.mme-journal.de

Table 2.  Mechanical properties of WP20/PVA and MFC15/PVA as compared to 3D printed PVA and mineralized composites prepared by multimate-
rial 3D printing of WP/PVA and MFC/PVA pastes together with water glass (WGsp).

Composition Young’s modulus [MPa] Tensile strength [MPa] Elongation at break [%] Vertical shrinkagea) [%]
PVA 570 ± 90 17 ± 3 33 ± 12 66 ± 4
WP20/PVA 1120 ± 130 30 ± 3 3.3 ± 0.5 56 ± 1
WP20/PVA_Gly 1160 ± 140 17 ± 4 1.5 ± 0.7 38 ± 3
WP20/PVA_WG 1530 ± 80 25 ± 3 4.1 ± 0.4 46 ± 7
WP20/PVA_WGsp 1550 ± 40 39 ± 3 3.5 ± 0.2 44 ± 4
MFC15/PVA 1300 ± 200 36 ± 4 3.8 ± 0.8 60 ± 2
MFC15/PVA_WG 1600 ± 200 35 ± 3 3.8 ± 0.9 53 ± 2
MFC15/PVA_WGsp 2400 ± 70 50 ± 10 3.1 ± 0.5 50 ± 3

a)The
vertical shrinkage was determined by measuring the height of the dried specimens as compared to the height of specimens in wet state obtained immediately after
completing printing prior to drying.

As shown in Figure  11, the enhancement of mechanical
properties of cellulose/PVA composites by WG mineraliza-
tion is accompanied by markedly lower flammability. After
exposure to a Bunsen burner flame for a duration of 20 s,
untreated MFC15/PVA immediately ignited and burned. In
sharp contrast, mineralized MFC15/PVA_WGsp, obtained by
multimaterial 3D printing together with water glass, is self-
extinguishing and exhibits charring. This behavior is in agree-
ment with reports in the literature using water glass additives
to render cellulose-based materials such as jute textiles flame
retardant.[58]
2.4. Printing of Cellulose/PVA Composites with
Programmable Shape Changes
The MFC15/PVA_Gly composite exhibits a glass temperature
(Tg) around 70 °C, as determined by DSC. While dry MFC15/
PVA_Gly was rigid and rather brittle at room temperature, it
was rendered rubbery by heating it above Tg or by immersing it
in water which functions as plasticizer. This temperature- and
water-induced change of Tg enables to program shape changes.
Chen et al. have exploited such temperature and water-induced
shape changes to fabricate crosslinked PVA as shape memory
tapes.[43] The 3D printed crosslinked cellulose/PVA composites
exhibited similar programmable shape memory behavior. Typi-
cally, MFC15/PVA_Gly samples of well-defined shapes were
prepared by 3D printing of aqueous WP/MFC pastes at room
temperature and subsequent crosslinking by immersing in
aqueous 40 wt% glyoxal solution followed by drying. Heating
above Tg allowed the programming of a temporary shape by
applying a stress followed by rapid cooling below Tg while
the stress was kept applied. The shape programming of the
3D printed MFC15/PVA_Gly tensile test bars is illustrated in
Figure 12. Their shape was changed by twisting them at 100 °C
(which is above Tg). Due to rapid cooling at constant strain, this
temporary twisted shape was programmed. The recovery of the
original shape was achieved in the dry state by heating the ten-
sile bars above Tg or by immersing them in water at 37 °C. The
process of shape programming and shape recovery is illustrated
in Figure 12. The time required for full shape recovery was
around of 90 min.

Figure 10.  The influence of post-treatment by crosslinking with glyoxal (Gly) and by mineralization with water glass (WG) on Young’s modulus and
tensile strength of 3D printed cellular WP20/PVA and MFC15/PVA composites as compared to the properties of cellulose/PVA composites prepared
by multimaterial 3D printing with spraying of water glass (WGsp).

Macromol. Mater. Eng. 2020, 305, 1900740 1900740  (8 of 12) © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 11.  Flammability of a) neat MFC15/PVA as compared to b) mineralized MFC15/PVA_WGsp after 20 s exposure to a Bunsen burner
flame.
3. Conclusion
Combining paper waste recycling with extrusion-based 3D
printing of aqueous cellulose pastes enables the facile fabrica-
tion of mineralized cellular cellulose composites with hierar-
chical pore architectures tailored for sustainable lightweight
construction. Key intermediates of 3D printing are cellulose
pastes produced by shear mixing of shredded untreated news-
paper waste (WP) or cellulose from other sources like MFC or
even paper pulp together with an aqueous solution of a pol-
ymer binder like PVA. By 3D dispensing of aqueous cellulose/
PVA print pastes, composites with a content of up to 28 wt%
WP can be obtained. The presence of cellulose fibers and
fibrils is essential to enable shear thinning of the pastes and
Figure 12.  Temperature- and water-triggered programmed shape
change of 3D printed MFC15/PVA_Gly, which was crosslinked with gly-
oxal. Above: Shape programming by twisting at 100 °C in the dry state.
Below: Shape recovery a) by heating to 100 °C or b) by immersing in
water at 37 °C.
Macromol. Mater. Eng. 2020, 305, 1900740 1900740  (9 of 12)
www.mme-journal.de
to achieve adequate dimensional stability of the resulting 3D
printed objects. Whereas 3D printing by fused filament fab-
rication and melt extrusion of WP with PVA thermoplastics
produces dense composites, the 3D printing of aqueous WP/
PVA pastes yields highly porous composites with pore sizes
varying between 50 and 200 µm accompanied by low densities
of around 0.8 g cm−3. This is attributed to the self-assembly
of cellulose fibers and fibrils during the 3D printing in con-
junction with water evaporation during drying. In spite of the
high porosity, high stiffness (Young’s modulus up to 2 GPa)
and tensile strength (up to 53 MPa) are achieved. Moreover,
hierarchical pore architectures with pores variable in different
length scales are readily tailored by printing honeycomb
or macroporous structures in which the size of macropores
is governed by computer assisted design and 3D printing
parameters, whereas micro- and nanopores result from the
self-assembly of the cellulose fibrils. Crosslinking by post-
treatment with glyoxal and mineralization with water glass
significantly improves water resistance of the printed objects
since PVA is rendered water insoluble by crosslinking. Instead
of time-consuming post-treatment by immersing printed
objects in aqueous water glass solution, mineralization is
readily achieved by multimaterial 3D printing in which 3D
extrusion of aqueous cellulose/PVA pastes is combined with
spraying of an aqueous water glass solution. Spraying of water
glass after completing 3D printing of pastes affords dense
silicate surface coating, as verified by SEM imaging, similar
to that obtained by immersing printed objects in water glass
solutions but without encountering the collapse of the inner
pore structure. In principle, the alternation of paste extrusion
and water glass spraying should enable the fabrication of mul-
tilayer composites exhibiting enhanced mechanical properties.
First attempts indicate that the mineralization needs to be
accelerated to prevent mixing of water glass and PVA. The 3D
printing of crosslinked WP/PVA composites offers attractive
prospects regarding the fabrication of thermo- and moisture-
responsive cellulose/PVA composites with programmable
shape change induced either by heating or by water addition.
This technology is attractive with respect to the development
of 4D printing with time as the fourth dimension for potential
applications in healthcare and medicine since the moisture-
induced shape change of the investigated materials can be
triggered under physiological conditions.
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Table 3.  Composition of WP/PVA print pastes used for 3D dispensing.
Composition m (PVA solution, 20 wt%) [g] m (WP) [g]
PVA neat 18.50
WP12/PVA 18.50
WP20/PVA 18.50
WP28/PVA 18.50
4. Experimental Section
Materials: PVA (88% degree of polyvinylacetate hydrolysis, weight
average molecular weight of 145 000–180 000 g mol−1) was purchased
from Acros Organics. Aqueous water glass solution (extra pure, Na2O
7.5–8.5%, SiO2 25.5–28.5%) was purchased from Merck KGaA. Glyoxal
(40% w/w aq. soln.) was purchased from Alfa Aesar. Paper waste
was derived from the local newspaper Badische Zeitung, and MFC
(WMFCQ_standard 3.5 wt% aq. dispersion) was kindly supplied by
Weidmann Fiber Technology. Cyclohexane (>99.5% AnalaR NORMAPUR
ACS) was purchased from VWR Chemicals.
Characterization: Rheological measurements of the viscosity were
performed using a Paar Physica UDS 200 plate–plate rheometer. The
used plate had a diameter of 2.5 cm. Measurements were carried out
at 25 °C in a frequency sweep from 100 to 1 rad s−1, with a constant
strain amplitude of 1% at a distance of 0.7 mm. The SEM was performed
using an Amray 1810 SEM, with an electron acceleration of 20 kV at a
working distance of 10 mm. Before measuring, the samples were coated
with an Au layer (10–20 nm) to prevent charging of the specimens.
For sample preparation of the investigated MFC dispersion, the
3.5 wt% MFC dispersion was diluted to 0.035 wt% followed by water
evaporation in a vacuum oven at 60 °C. The µ-CT images were taken
by Dr. Ralf Thomann at the Freiburg Institute for Interactive Materials
and Bioinspired Technologies (FIT) using a SKYSCAN 1272 X-ray µ-CT
by Bruker with an acceleration potential for the X-ray source of 20–110 kV
at 10 W. A CCD sensor was used for detection. DSC measurements were
performed using a Perkin Elmer’s Pyris 1, with a heating and cooling
rate of 10 K min−1. Tensile testing was performed on a Zwick Z005 (Ulm,
Germany, testing method DIN EN ISO 527-2, specimen type 5A) with
a drawing speed of 50 mm min−1. The mechanical properties such as
elastic modulus, tensile strength, and breaking elongation were extracted
from measurements at room temperature by taking the statistical average
of five test specimens (5A). The pycnometric measurements were carried
out using a 10 mL glass pycnometer filled with cyclohexane and 0.5–1.3 g
of pieces from 3D printed tensile test specimens. The detected weights
were measured with an analysis scale with an accuracy of ±0.1 mg.
Preparation of WP: For the preparation of WP, which was used as
shear thinning additive, the local newspaper “Badische Zeitung” was
shredded in a paper shredder to produce 0.5 cm thick stripes. Afterward,
a 2 wt% aqueous WP suspension was prepared using 10 g shredded
paper waste and 490 g deionized water. The mixture was blended using
a Braun Type 4169 hand blender with 150 W for 3 min in a 1 L beaker
followed by water removal via freeze drying. A gray spongy solid material
was obtained. For better processing, the lumpy solid was milled using
a Z200 centrifugal mill by Retsch at 12 000 RPM using a 0.5 mm sieve.
Preparation of Neat PVA and WP/PVA Pastes for 3D Dispensing: PVA
(40.00 g) was dissolved in deionized water (160 mL) at 95 °C and stirred
for 1 h using a KPG stirrer. Then, the resulting 20 wt% solution was
cooled down to room temperature and various amounts of WP were
added to 18.50 g of the highly viscous PVA solution and homogenized
by hand using a spatula. For every composition, 15.00 g of the resulting
gray dispersions were fed into a 30 cc Nordson EFD dispensing
cartridge. Table 3 shows the compositions of all WP/PVA print pastes.
Preparation of MFC15/PVA Paste for 3D Dispensing: For the preparation
of the MFC15/PVA paste, PVA (20.00 g) was given to a 3.5 wt% aqueous
dispersion of MFC (100.00 g). The resulting MFC content in the aqueous
print paste was 2.9 wt%, while the MFC content in the dried MFC15/PVA
Macromol. Mater. Eng. 2020, 305, 1900740 1900740  (10 of 12)
www.mme-journal.de
WP content in paste [wt%] WP content in solids [wt%]
0 0 0
0.50 2.7 11.9
0.92 4.7 19.9
1.44 7.2 28.0
composites was 14.9 wt%. The mixture was kept at 95 °C for 1 h and
stirred using a KPG stirrer. Then, the resulting dispersion was cooled
down to room temperature, 15.00 g each was filled into a 30 cc Nordson
EFD dispensing cartridge.
Extrusion-Based 3D Printing: 3D dispensing was performed using
a second generation 3D Bioplotter from EnvisionTEC. Both, slicing
and the control of the printing process were carried out using the
Primcam 2.99 ß4 Software. Material extrusion was pneumatically
controlled with a maximum air pressure of 5.0 bar, which was adjusted
for each composition to obtain a constant material flow. The following
parameters were kept constant for every composition: print speed xy:
400 mm min−1; print speed z: 350 mm min−1. Preflow time, post-flow
time, corner delay (each 0.01 s), filling pattern (90°), and outer contour
(activated) and layer thickness (0.67 mm). Applying these settings,
type 5A test specimen with a total height of 2 mm was obtained after
printing three layers. The infill of the 3D printed specimen was 100%.
All prints were performed at room temperature using Nordson EFD
dispensing tips with a diameter of 0.41 mm. Specimens for tensile tests
and shape memory experiments were printed based on a CAD model
of a 5A test specimen. In compositions without any post-treatment, the
3D objects were printed onto a conventional photocopy film while post-
treated samples were printed into a petri dish. Table 4 shows the varied
parameters during 3D dispensing referred to the used print pastes.
Glyoxal Crosslinking: Crosslinked 3D objects were 3D printed into an
open petri dish. After 3D dispensing, a 40% aqueous glyoxal solution
was given into the petri dish. The immersed objects were kept completely
covered with glyoxal solution for 3 days at RT at pH = 3–4. After 3 days,
the crosslinked objects were dimensionally stable to be taken out of the
solution by a tweezer and were predried at room temperature. Final
drying was achieved in a vacuum oven for 18 h at 60 °C.
Water Glass Mineralization: Analogous to crosslinked compositions,
3D printed objects that were mineralized with water glass were 3D
printed into an open petri dish. After 3D dispensing, a 35% aqueous
water glass solution was given into the petri dish and the immerged
objects were kept completely covered with water glass solution for 3
days at RT at pH = 11–12. After 3 days, the water glass was removed
and the samples were predried at room temperature. Final drying was
achieved in a vacuum oven for 18 h at 60 °C.
Multimaterials Printing by Water Glass Spraying Combined with Paste
Extrusion: For the fabrication of multilayer composites by water glass
spraying, 3D dispensing of 5A tensile test specimens was carried out at
RT into an open petri dish. With a layer thickness of 0.67 mm, three layers
were printed for each specimen to achieve a 2 mm high 5A specimen.
Table 4.  Varied printing parameters for WP/PVA and MFC/PVA print for
3D dispensing.
Composition Air pressure for material Strand distance
extrusion [bar] xy [mm]
PVA neat 1.5 1.2
WP12/PVA 3.0 1.2
WP20/PVA 3.4 1.2
WP28/PVA 3.8 0.9
MFC15/PVA 3.3 1.0
© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
After each layer, the 3D dispensing was manually paused for about 30 s.
During this break, the print head stayed about 10 cm above the printed
object and spraying of a volume of about 1 mL water glass solution (35%
aqueous solution) onto the printed layer was carried out using a hand-held
dispenser. After water glass spraying, the 3D dispensing was continued
and the procedure was repeated two times. Immediately after completing
this procedure, the samples were predried at room temperature. Final
drying was achieved in a vacuum oven for 18 h at 60 °C.
Flammability Test: For flammability tests, the shoulders of 3D printed
tensile test specimens were cut off and the reduced section of the
specimen was attached horizontally in a fume box using a lab clamp.
The end of the attached bars was held into the flame of a Bunsen burner
(T ≈ 1500 °C) for 20 s. After removal of the heat source, the fire behavior
was recorded with a camera. The test was carried out with the materials
MFC15/PVA and MFC15/PVA_WGsp.
Shape Memory Experiments: Shape memory experiments were
performed with glyoxal crosslinked tensile test specimens of the
composition MFC15/PVA_Gly. Since the dry samples were too brittle
for shape programming at RT, the specimens were heated up and
kept at 100 °C for 5 min with a heat gun to become elastic. Afterward,
the samples were twisted by applying a force at both ends of the
specimens with two tweezers. After the specimens cooled down to
room temperature at applied stress, the tweezers were removed and the
programmed shape was preserved. Temperature-induced shape recovery
was carried out by placing a twisted specimen in an oven at 100 °C for
30 min. For the water-induced shape recovery, a twisted sample was
immerged into water at 37 °C for 90 min.
Acknowledgements
The authors gratefully acknowledge financial support of the Baden-
Württemberg Stiftung GmBH (project 4DmultiMATS) with respect to
medical application and 4D printing. Furthermore, the authors thank
BASF SE for the support of the research on 3D printing of sustainable
construction materials within the frame of the Joint Research Network
on Advanced Materials and Systems (JONAS). The authors are also
thankful to Kris Bielefeld, Ralf Thomann, Marcel Zimmermann, Klaus
Hasis, Andreas Warmbold, Wildone Teqolli, and Eveline Konrat for their
enthusiastic support. The donation of MFC dispersions by Weidmann
Fiber Technology from Rapperswil-Jona, Switzerland, is gratefully
acknowledged. Correction added on 24 March 2021, after first online
publication: Projekt Deal funding statement has been added.
Open access funding enabled and organized by Projekt DEAL.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
3D printing, additive manufacturing, cellulose, paper, recycling
Received: October 31, 2019
Revised: January 27, 2020
Published online: March 20, 2020
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