Carbohydrate Polymers 207 (2019) 297–316

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Current advances and future perspectives of 3D printing natural-derived T

biopolymers
⁎
Jun Liua, Lushan Sunb, Wenyang Xuc, Qianqian Wanga, Sujie Yua, Jianzhong Suna,
a
Biofuels Institute, School of the Environment and Safety Engineering, Jiangsu University, 212013, Zhenjiang, China
b
Institute of Textiles and Clothing, The Hong Kong Polytechnic University, Hong Kong, China
c
Johan Gadolin Process Chemistry Centre, c/o Laboratory of Wood and Paper Chemistry, Åbo Akademi University, Turku, FI-20500, Finland

A R T I C LE I N FO A B S T R A C T

Keywords: 3D printing enables the complex or customized structures production in high speed and resolution. However, the
3D printing lack of bio-based materials with user-defined biochemical and mechanical property is a significant barrier that
Additive manufacturing limits the widespread adoption of 3D printing for products fabrication. Development of eco-friendly natural-
Biopolymers derived biopolymers for 3D printing technologies and their promising application in different areas are of huge
Biomass
academic, and environmental interests. This paper reviews the state-of-the-art in terms of 3D printing technology
Biomedical application
using natural-derived feedstocks, including lignocellulose, starch, algae, and chitosan-based biopolymers.
Special consideration is given to the development of lignocellulosic materials, i.e. cellulose, hemicellulose,
lignin, and their derivatives as 3D printing feedstocks. A strategical development roadmap with identified
material property requirements, key challenges, as well as possible solutions was proposed. It serves as guideline
aiming to explore natural-derived biopolymers as novel feedstocks for different 3D printing technologies that
will be potentially applied in various areas.

1. Introduction
3D printing, also known as additive manufacture (AM), is a process
for constructing 3D physical objects from digital models through the
successive layer-by-layer deposition of materials such as plastic, metal,
ceramics, or even living cells (Bhatia & Ramadurai, 2017). The 3D
printing concept was first proposed by Charles W. Hull, using a stereo-
lithography to make polymer objects in the 1980s. Nowadays, there
many different 3D printing or AM technologies which have been di-
vided into several process categories according to the standard of ISO/
ASTM 52921:2013 as in shown in Fig. 1, which mainly include the
material extrusion, material jetting, binder jetting, powder bed fusion,
direct energy deposition, vat photo-polymerization, and sheet lamina-
tion. Depend on the printing method and the inks formulation, objects
are fabricated in a successive layer-by-layer fashion by dispensing the
material with an extruder, by using chemical agents (e.g. binder) or a
laser (sintering/melting) (Kalaskar, 2017). Fig. 1 shows the 3D printing
principle, classification of 3D printing systems and the specific printing
technologies, as well as the available materials for each printing ap-
proach. For a detailed review of different 3D printing technologies, it is
available for readers to read further relevant reviews by Gao et al.
(2015), Huang, Leu, Mazumder, and Donmez (2014), Mandrycky,
Wang, Kim, and Kim (2016), and Wong and Hernandez (2012).
3D printing is a growing technology that makes a revolutionary
impact on products fabrication for applications in areas like healthcare
and medicine, aeronautics and space, automotive, food industry, art,
textile and fashion, architecture and construction, which has drawn an
increasing attention globally (Melchels et al., 2012; Ozbolat, Peng, &
Ozbolat, 2016; Shishkovsky, 2016; Vanderploeg, Lee, & Mamp, 2016;
Ventola, 2014). However, there are still a lot of challenges need to
overcome before the 3D printing technology can be adopted as a
common fabrication technology and can achieve its full potential.
Limited variety of available, environmentally friendly, and printer-
friendly materials is a key barrier to the wide-scale adoption of 3D
printing technologies.
In line with the current focus on the sustainable economy, the ex-
ploring of natural-derived and renewable biopolymers, instead of those
fossil oil-based plastics, for various products fabrication has received
tremendous attention. Biomass from marine, woody and agricultural
residuals, the most abundant renewable feedstocks on earth, has
showed a promising potential as alternatives to fossil resources (Bhatia
& Ramadurai, 2017; Fernandes, Pires, Mano, & Reis, 2013; Liu,
Korpinen, Mikkonen, Willför, & Xu, 2014; Zhang, Liu, Cui, & Chen,
2015). Development of biomass-based materials instead of fossil oil-

⁎
Corresponding author.
E-mail address: jzsun1002@ujs.edu.cn (J. Sun).

https://doi.org/10.1016/j.carbpol.2018.11.077
Received 15 June 2018; Received in revised form 21 November 2018; Accepted 23 November 2018
Available online 24 November 2018
0144-8617/ © 2018 Elsevier Ltd. All rights reserved.
J. Liu et al.
Fig. 1. Categories of 3D printing technologies and commonly used materials. Modified from Wijk and Wijk (2015), Copyright (2015), IOS Press.
based plastics for different 3D printing technologies provides an op-
portunity to realize a truly sustainable and recycling economy (Wijk &
Wijk, 2015). By integration with the 3rd generation of biorefinery
concept, each component of the biomass can be extracted with their
sophisticate native structure and tailored into versatile 3D printing
materials in different forms for addictive manufacturing of variety of
high-value-added products or a further application in various areas,
such as healthcare and medicine, aeronautics and space, automotive,
food industry, art, textile and fashion, architecture and construction.
Using natural-derived biopolymers as 3D printing feedstocks, e.g. cel-
lulose, hemicellulose, lignin, starch, alginate, chitosan, and derivatives
of them, not only meet the demand for sustainability, but also truly
reduce a possibility in the side/negative effects associated with some
synthetic polymers in biomedical applications, such as degradability,
recyclability, harmful breakdown products, released additives, and
decreased cell attachment (Chia & Wu, 2015; Guvendiren, Molde,
Soares, & Kohn, 2016; Li et al., 2014; Park, Lih, Park, Joung, & Han,
2017).
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Carbohydrate Polymers 207 (2019) 297–316
This paper reviewed the state-of-art in the development of natural-
derived biopolymers, with a main focus on the polysaccharides, such as
cellulose, hemicellulose, and their derivatives or composites, for dif-
ferent 3D printing technologies and their potential applications in dif-
ferent fields. The aims are to identify some opportunities for replace-
ment of fossil oil-based plastics with natural-derived biopolymers for
3D printing, and further to promote a transformation of product de-
velopment and their manufacturing in a sustainable way. We first
outline the material properties that are key for different targeting ap-
plication areas, mainly including medicine and pharmacy, customized
food fabrication, textile and apparel products, followed by re-
presentative research and development of natural-derived biopolymers
for 3D printing. The current technological challenges and future per-
spectives of 3D printing with natural-derived biopolymers for applica-
tion in different areas are also proposed.
J. Liu et al.
2. Key properties required for 3D printing with natural-derived
biopolymers in different areas
2.1. Medical and pharmaceutical products
3D printing offers significant advantages for medical and pharma-
ceutical applications due to the ability to fabricate patient specific and
custom-made medical products, equipment, and drugs (e.g. dosage
forms, release profiles, and dispensing). Current and future research
interests in the 3D printing of biomedical and pharmaceutical products
mainly include: 1) tissue and organ fabrication; customization of
prostheses, implants, and anatomical models; 2) personalized drug
dosage forms, drug delivery, drug screening and discovery in pharma-
ceutical research (Derby, 2012; Melchels et al., 2012; Murphy & Atala,
2014; Ventola, 2014; Zhang, Fisher, & Leong, 2015). 3D printing
technologies for medical and pharmaceutical applications would
mainly involve with extrusion-based printing, inkjet-based printing,
particle fused-based 3D printing, and light-assisted 3D printing
(Guvendiren et al., 2016; Kalaskar, 2017). Different printing ap-
proaches and their targeted applications will certainly pose some dif-
ferent requirements for material properties. However, all biopolymers
for 3D printing application in medicine and pharmacy need to meet a
series of strict requirements, considering both physiological conditions
and their associated interactions with the local body environment
(Kalaskar, 2017). Fig. 2A shows the key material property requirements
for 3D printing applications in medicine and pharmacy. In general, the
material property requirements for 3D printing applications in
Fig. 2. Material property requirements and the associated factors to be considered for bioprinting (A) and 3D food printing (B). Adapted with permission from
Roopavath and Kalaskar (Kalaskar, 2017), Copyright (2017), Elsevier; (Godoi et al., 2016), Copyright (2016), Elsevier.
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Carbohydrate Polymers 207 (2019) 297–316
medicine and pharmacy include, but not limited to, printability, bio-
compatibility, degradability (safe degradation byproducts and good
degradation kinetics), exhibiting tissue biomimicry, and appropriate
mechanical properties (Derby, 2012; Guvendiren et al., 2016; Murphy
& Atala, 2014).
Materials should have a sound processability, and are printer-
friendly, e.g. shear thinning behavior and high zero shear viscosity,
allowing accurate and easy 3D plotting of constructs with fine resolu-
tion, high shape fidelity, and structural stability (Kyle, Jessop, Al-
Sabah, & Whitaker, 2017; Sultan, Siqueira, Zimmermann, & Mathew,
2017).
Biocompatibility regarding the cellular and tissue compatibility of
the ink components, printed structure, any leachables or degradation
by-products from the printed structure or the material should be eval-
uated (Liu, Willför, & Mihranyan, 2017). Normal biocompatibility tests
include in vitro tests of DNA damage, cytotoxicity, cell proliferation,
quantification of specific proteins, as well as necessary in vivo tests
according to the medical device categorization by tissue contact and
contact duration (Ratner, Hoffman, Schoen, & Lemons, 2013).
For the scaffolds that are not aimed for permanent implants, the
printed structures are supposed to degrade into biocompatible by-pro-
ducts in a controlled manner, permitting the cells to produce their own
extra cellular matrix or allowing the incorporated components to reach
the desired release profiles (Axpe & Oyen, 2016; Ursan, Chiu, & Pierce,
2013).
Tissue biomimicry poses requirements for the printed constructs not
only mimic the natural shape of the organs and tissues, but also the
J. Liu et al.
complex, heterogeneous nature of those tissues, including the desired
biological functionality, sufficient strength and stiffness to maintain
structural integrity, macro- and micro-porous architecture, which turns
into the key challenges for 3D printing biopolymers for biomedical
application, especially in tissue engineering (Munaz et al., 2016; Zhang,
Fisher et al., 2015). More detailed requirements of the 3D printing
materials or the printed structures should be considered for a specific
target application and its printing approach.
2.2. Customized food fabrication
3D printing for food fabrication offers opportunities to manufacture
food products with customization in shape, color, flavor, texture and
even nutrition (Sun et al., 2015). Generally, materials for 3D food
printing should be edible, printable, rigid and stiff enough to support its
own weight and the weight of subsequently deposited layers without
deformation or shape change, and resist to post-processing (e.g. baking,
cooking, and frying). Fig. 2B shows the general material requirements
for 3D food printing, which include printability, applicability, and post-
processing feasibility. Controlling the physical-chemical, rheological,
structural and mechanical properties of the materials is the key to en-
sure the accurate precise, and smooth printing process (Godoi, Prakash,
& Bhandari, 2016; Lin, 2015; Sun et al., 2015). A variety of natural-
derived biopolymers such as cellulose, hemicellulose, pectin, starch,
alginate, agarose, and chitosan show potential to be utilized in 3D food
printing owing to their nontoxicity, edibility, high abundancy, bioac-
tivity (e.g. serve as dietary fibers), and long history of utilization in
traditional food production (Alec, 2016; Godoi et al., 2016; Lille,
Nurmela, Nordlund, Metsä-Kortelainen, & Sozer, 2018).
Currently, four types of 3D printing approaches available for 3D
food printing, including extrusion based printing, selective sintering
printing (with laser or hot air), binder jetting, and inkjet printing (Liu,
Zhang, Bhandari, & Wang, 2017). Each printing method poses different
requirements for the materials. Therefore, more requirements upon the
3D food printing of biopolymers depend on the printing method and the
final products. Natively printable materials like hydrogels, starch,
chocolate, and cake frosting can be printed through an extruder, while
some non-printable food by nature such as meat, vegetables, and rice
have to be processed into the form of powder or paste before subjecting
to 3D printing. Biopolymers in the form of hydrogel or paste-like slurry
with shear thinning behavior are beneficial for the extrusion based 3D
food printing, as they possess not only relative low viscosity upon shear
stress to be easily extruded out from nozzle, but also suitable yield
stress and elastic modulus upon the departure from the nozzle to
maintain a high shape fidelity (Godoi et al., 2016; Liu, Zhang, Bhandari,
Wang, 2017). The main requirements for the selective sintering and
binder jetting based printing of food are that the materials should be
edible free-flowing powder and have no tendency to agglomerate or to
adhere to contact surface. For the selective sintering, the materials
should have appropriate thermal stability, should be able to fuse to-
gether without decomposition during laser scan (Liu, Zhang, Bhandari,
Wang, 2017). Generally, materials for inkjet printing should have low
viscosity to be easily ejected through the print head.
2.3. Textile and apparel products
3D printing technologies that offer mass customization of products
on-demand by freedom of shape and design are increasingly being ex-
plored for textile industry to create parts that would be impossible to
produce with conventional techniques (Sun & Zhao, 2017, 2018). Fully
printed shoes, dresses, and fashion collection were presented and drawn
increasing interest of designers over the last few years. Generally, ap-
parel and textile products require sufficient flexibility, resilience, and
tensile strength in accommodating to wearer’s comfort and body
movement, which are, unfortunately, hard to meet with most of the
currently available materials (Martens & Ehrmann, 2017). Therefore,
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Carbohydrate Polymers 207 (2019) 297–316
increasing research turn to focus on the application of 3D printing to
functionalize and modify different types of textile substrates.
Marrying different types of fabrics and 3D printing offers the pos-
sibility to develop innovative multicomponent smart textiles by de-
position of functional polymers or intelligent materials onto textiles
without compromising on quality and flexibility of the fabric
(Grimmelsmann, Meissner, & Ehrmann, 2016; Korger et al., 2016). 3D
printed smart textiles can find many applications such as wearable
electronics with heart-rate monitoring and high speed communications,
wearables with protection purposes for soldier, firefighters and astro-
nauts, unique sportswear that manages body temperature, smart ban-
dages, and virtual reality gloves (Gao et al., 2017; Hashemi Sanatgar,
Campagne, & Nierstrasz, 2017; Hashemi Sanatgar, Cayla, Campagne, &
Nierstrasz, 2017).
The FDM deposition is the most common approach to functionalize
textiles with thermoplastic polymers, e.g. ABS, PLA and Nylon. Direct-
write has been applied to print materials that do not possess the ther-
moplastic properties required in the FDM method, e.g. cellulosic ma-
terials. SLS printing of different types of powdered materials, e.g.
thermoplastic polyurethane (TPU), could be adopted to fabricate soft
fabrics for a fashion application (Beecroft, 2016; Tenhunen et al.,
2018).
Polymer deposition depends strongly on the combination of textiles
and polymers. For effective deposition of polymers onto fabrics, areas
that need to be considered include: (a) sufficient mechanical properties
of the printed objects and the interaction with fabrics; (b) drapability of
the printed fabric for free movement; (c) flexibility of the printed fab-
rics when subject to daily use; (d) washability (Hashemi Sanatgar,
Campagne et al., 2017; Hashemi Sanatgar, Cayla et al., 2017). It is
unequivocal that further research of new materials, compatibility be-
tween fabrics and polymer, polymer-textile adhesion and polymer de-
position technology would benefit the production of individualized or
customized functional textiles as well as apparel.
3. 3D printing of natural-derived biopolymers
3.1. 3D printing of lignocellulosic biomass materials
The main components of lignocellulosic biomass, including cellu-
lose, hemicellulose, and lignin, represent the most abundant en-
vironmentally friendly biopolymers with the properties of sustain-
ability, non-toxicity, biocompatibility, and biodegradability (Fig. 3)
(Fernandes et al., 2013; Liu, Willför, & Xu, 2015). However, the physic-
chemical properties of lignocellulose, e.g. infusibility and insolubility in
common solvents, limited their application in the 3D printing process.
Hence, a variety of strategies to modify the lignocellulosic biomass or to
update the 3D printing technologies have been adapted to explore the
lignocellulosic biomass as a potential feedstock for 3D printing (Fig. 3).
A list of 3D printing natural-derived biopolymers, with the focus on the
biomass polysaccharides, is tabulated in Table 1 and further discussed
in the following sections.
3.1.1. 3D printing of native cellulose-based materials
Cellulose, a homogeneous polysaccharide consists of linear β-(1→
4)-glucan with intra- and intermolecular hydrogel networks (Fig. 3), is
the most abundant renewable and biodegradable biopolymers world-
wide. Development of cellulose-based materials as a new type of feed-
stocks for 3D printing technologies would open a new window to ex-
plore cellulose materials. Currently, the most intensively studied native
cellulose-based 3D printing material is the cellulose nanofibrils (CNF)
hydrogel. The CNF hydrogel-based inks are biocompatible and can
mimic the microenvironment of extracellular matrix (ECM), which,
therefore, has been recently considered in biomedical applications (Liu,
Cheng et al., 2016; Liu, Chinga-Carrasco et al., 2016). However, the
high hydrophilicity and the inherently entangled state of CNF limited
the increase of ink concentration at a given viscosity and storage
J. Liu et al.
Fig. 3. Molecular structures of cellulose and representative hemicelluloses, as well as their representative 3D printed structures. 3D printed structures are adapted
with permission from: Müller et al. (2016), Copyright (2016), Springer; (Schütz et al., 2017), Copyright (2015), John Wiley and Sons; (Pattinson & Hart, 2017),
Copyright (2017), John Wiley and Sons; (Markstedt et al., 2014), Copyright (2014), Mary Ann Liebert.
modulus. Efforts have been carried out to directly dissolve or utilize
native cellulose in other forms.
Native cellulose cannot be readily dissolved in common solvent
systems due to the strong H-bond network and crystalline structure.
Ionic liquids (ILs) are a new class of cellulose “green” solvents with low
melting temperature. Dissolution of cellulose is achieved by disruption
of native cellulose H-bond network with new formed H-bonds between
cellulose and anions, and the hydrophobic interactions with cations.
Anti-solvent, such as water, ethanol, and acetone, can be added to re-
generate cellulose and recycle the ILs (Gupta & Jiang, 2015). Markstedt,
Sundberg, and Gatenholm (2014) dissolved different cellulose mate-
rials, including bacterial cellulose (BC), microcrystalline cellulose
(MCC), and dissolving pulp, in an ILs (EmimAc) with solid concentra-
tion up to 4% and applied for direct ink writing (DIW) printing. Com-
plex patterns of 2D structures and multilayered cylinders structures
were printed and coagulated with water. However, the spatial resolu-
tion of the printed structure and the recycle of the ILs still need to be
addressed.
Cellulose nanocrystals (CNC) prepared from acids hydrolysis may
offer advantages over the cellulose ILs dissolution and the CNF in terms
of the increase of concentration at a given rheology requirement for 3D
printing. Siqueira et al. (2017) dispersed the CNC in water to prepare
different concentration of suspensions/gels inks (0.5–40%) for DIW and
yielded cellulose-based structures with high degree of CNC particle
alignment along the printing direction, offering the opportunity to print
cellulosic architectures with tailored mechanical properties.
Native cellulose can also be utilized in 3D food printing by serving
as dietary fiber, bulk filling agent, or rheological modifying ingredients,
and reinforcing ingredient owing to its indigestibility, excellent me-
chanical performance, and high viscosity of native cellulose. Lille et al.
(2018) incorporated the CNF gel in a 3D printing ink formula as re-
inforcing ingredient for the development of healthy customized 3D
printed foods. CNF was found to improve the shape stability of the
printed structures and to decrease the hardness of the dried objects,
revealing its potential for 3D printing healthy fiber-rich and structured
foods.
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Carbohydrate Polymers 207 (2019) 297–316
3.1.2. 3D printing of cellulose derivative-based materials
The super-molecular structure of cellulose, i.e. high crystallinity
degree and rigid intra/intermolecular hydrogen bond networks, re-
stricts its application. However, the abundant hydroxyl groups on the
cellulose surface opens opportunities for chemical modification or
functionalization, such as esterification, etherification, selective oxi-
dation, graft copolymerization, and intermolecular crosslinking reac-
tion, bringing novel opportunities to exploit them for various applica-
tions such as in food, cosmetic, medicine and pharmacy (Liu, Willför
et al., 2015; Qi, 2017).
Interfacial compatibility problem between polar native cellulose
and nonpolar polymers matrix is the key limitation for the application
of native cellulose which has excellent mechanical performance as re-
inforcing agents in composites manufacture. To improve the compat-
ibility with the PLA, surface-modification of cellulose was conducted
using a titanate coupling agent via coordination exchange (neoalkoxy)
or solvolysis (monoalkoxy) (Murphy & Collins, 2016). The modified
cellulose was found to improve dispersion and interfacial adhesion
between the cellulose and the PLA, leading to the higher mechanical
strength of the composite filament than the neat PLA alone. Porous
scaffold prototypes were successfully printed with FDM using the cel-
lulose reinforced PLA filaments, offering the opportunity for rapid
production of fully degradable biocomposite 3D prototypes for appli-
cations in the biomedical, automotive, and construction sectors.
Similarly, to improve the dispersibility of CNC and interfacial
bonding after DIW and UV polymerization, Siqueira et al. (2017) ap-
plied acetylation reaction for CNC surface modification by using me-
thacrylic anhydride. The modified CNC was dispersed in a mixture of
photopolymerizable monomer and photoinitiator. After DIW printing
and curing, the yielded structures were found to have a high degree of
CNC particle alignment along the printing direction, providing the
opportunity to print cellulosic architectures with programmable re-
inforcement along prescribed directions.
(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO)-mediated oxida-
tion and carboxymethylation are two common approaches to prepare
CNF by introducing negative charges on the cellulosic fiber surface
followed by mechanical processing (Liu et al., 2014). The yield CNF
 Table 1
Natural-derived biopolymers for 3D printing and their potential applications.
Biobased printing Printing/solidification approach
materials
BC/MCC/Dissolving pulp Bioprinting /nonsolvent (water)
coagulation
CNC/acetylated CNC DIW/DIW + UV photopolymerization
CNF/alginate Bioprinting/crosslinking with
100 mM CaCl2
302
CNF/alginate/hyaluronic Bioprinting/crosslinking with
acid 100 mM CaCl2, or 0.001% (v/v) H2O2
CNF/Alginate sulfate Bioprinting/ crosslinking with
100 mM CaCl2
CNF/Alginate/Glycerin VTT’s microdispensing system/
crosslinking with 90 mM CaCl2
CNF Bioprinting/ crosslinking with 0.05 M
CaCl2; Bioprinting; Extrusion-based
3D printing
Ink formulation
Dissolution of cellulose in ionic liquid
(EmimAc), 1-4%.
Aqueous CNC suspension or gel, 0.5-40% /
10% or 20% acetylated
CNC + photopolymerizable
monomer + photoinitiator.
Human chondrocytes laden CNF-alginate
bioinks;
Human bone marrow-derived stem cells and
human nasal chondrocytes-laden CELLINK®.
Living adipocytes-laden CELLINK®/
CELLINK-H (CNF: hyaluronic acid, 80:20,
70:30);
Human-derived induced pluripotent stem
cells (iPSCs) and irradiated human
chondrocytes- laden CNF-alginate (60:40)/
hyaluronic acid composite inks.
Bovine chondrocytes-laden CNF-Alginate
sulfate bioinks (4.2:1, v/v)
Hydrogels composed of biofunctionalized
CNF, alginate, and glycerin.
TEMPO-mediate oxidized CNF, 0.95% /
Carboxymethylated and periodate oxidized
CNF, 3.9%;
Carboxymethylated CNF(2%) / CNF-carbon
nanotube conductive ink;
CNF, starch, milk powder, rye bran, oat/faba
bean protein.
Printed structure
Complex patterns of 2D
structures, multilayered
Cylinders.
Grids and block (8 layers).
Grids, solid disc, human ear
and sheep meniscus shaped
structures;
patient-specific auricular
constructs with 50% open
porosity. Lattice-structure;
Lattice-shaped constructs
Gridded structure with three
layers;
Six-layer grids
Grid-like constructs (2–4
layers)
Grid structures
Grid structure, 3D scaffold
(9 layers);
Hydrogel / aerogel /
conductive films;
Squares filled with diamond-
like structures.
J. Liu et al.
Potential applications Achievements/comments References
Spatially tailored 3D gels Printed structure needs a Markstedt et al. (2014)
or membrane structures nonsolvent for coagulation;
production. Vertical supports are needed for
multilayers structures; printing
spatial resolution need to be
enhanced.
Cellulose-based Programmable reinforcement Siqueira et al. (2017)
architectures with tailed owing to the CNC particle
mechanical properties. alignment along the printing
direction.
Cartilage tissue Forces during mixing and the cross- Markstedt et al. (2015),
engineering linking process could result in the Martínez Ávila et al.
decrease of cell viability. Cells (2016), Möller et al.
embedded in thick structure may (2017)
have oxygen/nutrient/waste
diffusion problems.
Ca2+ may have negative effect on
the cell viability. Loss of Ca2+
during long-term culture may
weaken the strength of the
structure.
Clinically demonstrated the
neocartilage formation and
stability of the 3D bioprinted cell-
laden scaffolds in vivo.
Adipose tissue Incorporation of HA lead to the Henriksson et al. (2017),
engineering; cells to releases more angiogenic Nguyen et al. (2017)
Cartilage lesions growth factors which could be
treatment benefit the co-culture of vascular
cells for future printing of blood
vessel structures for gas and
nutrient influx in the printed tissue;
The co-printed irradiated human
chondrocytes stimulates the iPSCs
differentiation.
Cartilage tissue The biological performance of the Müller et al. (2016)
engineering cells was highly dependent on
printing conditions, e.g. the nozzle
geometry.
Biomedical devices, The biofunctionalized CNF-alginate Leppiniemi et al. (2017)
wearable sensors, and hydrogel provide a platform for
drug-releasing materials immobilization of bioactive
components in the 3D printed
structure.
Wound dressing; Printed structures have limited Håkansson et al. (2016),
Packaging, textiles, resolution. CNF hydrogels Lille et al. (2018), Rees
biomedical devices, and collapsed and no defined tracks et al. (2015)
furniture with could be observed;
conductive parts; Incorporation of functional
Healthy, fiber-rich, and ingredients into the CNF-based ink
structured foods. for 3D printing offers opportunities
to construct a vast verity of new
applications, e.g. functional
(continued on next page)
Carbohydrate Polymers 207 (2019) 297–316
 Table 1 (continued)
Biobased printing Printing/solidification approach
materials
Cellulose acetate Modified FDM with filament extruder
replaced by a capillary nozzle.
Methylcellulose-alginate Bioplotting, crosslinked with Ca2+
Titanate surface modified FDM
cellulose
Thermoplastic cellulose Extrusion based 3D printing, DIW
derivatives,
hydrogels, cellulose-
based plastics and
pulp fibre composites
Hemicelluloses (GGM), FDM
303
PLA
Starch Particle binding, post-processing to
remove unbound powders and to
enhance mechanical strength;
FDM + enzymatic crosslinking /
Extrusion-based 3D printing
PLA FDM + cold atmospheric plasma post-
processing / FDM + surface coating
Alginate, oxidized Bioprinter, custom-made, piston-
alginate driven deposition system, on a
temperature-controlled plate at 4 °C,
crosslinked with Ca2+;
A dual syringe extrusion-based 3D
printer. Three crosslinking stages with
80 mM CaCl2, 100 mM CaCl2, 60 mM
BaCl2 for the purpose of enhancing
printability, rigidity after printing,
and long-term stability;
Ink formulation Printed structure
Dissolution of cellulose acetate in acetone Eyeglass frames, rose,
(25-35%). Antimicrobial agents. forceps with customized tips
containing antimicrobial
agents.
Methylcellulose-3% alginate Scaffolds
Titanate surface modified cellulose (0-5%), Porous scaffold prototype
PLA.
Cellulose hydrogel, thermoplastic cellulose Self-standing objects,
derivatives, cellulose-based plastics and pulp surface structures on fabrics.
fibre composites
Blends of GGM and PLA with varied ratio up 3D scaffold (10 layers)
to 25% of GGM.
A three-powder blend consists of 50% corn Porous cylindrical and
starch, 30% dextran, 20% gelatin, and water- rectangular scaffolds, solid
based binder; cylinder scaffolds;
Sodium caseinate, apple pectin, potato Multi-layer lattice structure
starch, sucrose / Potato starch, mashed / Apple, heart-shape, bear
potatoes / Potato starch, lemon juice head, π, and Chinese
character / Cylinder
structure, anchor, lizard,
star, cycle, and pyramid
shape.
PLA, biomacromolecules (e.g. protein, Scaffolds
growth factor, RGD), bioactive filler (e.g.
hydroxyapatite, bioactive glass)
Sodium periodate oxidized alginate, RDG Lattice structure,
peptides-conjugated alginate; 5 х 5 dot array;
Alginate, Human glioma U87-MG cells-laden Branched vascular
alginate at 4% w/v; structures;
NIH 3T3 mouse fibroblast cells-laden Square grid patterns,
alginate solution, 1-3% w/v; dumbbell-shaped structure,
Porcine aortic valve interstitial cell (VIC) and Tri-leaflet heart valves;
human aortic root smooth muscle (SMS) cell- Three layers lattice
laden alginate (5%)/gelatin (6%) hydrogels; structure;
Pre-crosslinked alginate and composite ink 7-layer
Potential applications
Customized medical
instruments
Regenerative therapy,
e.g. fat, cartilage, defects
at tissue interfaces.
Biomedical, automotive,
and construction.
Clothing design and
manufacture, Medical
science.
Biomedical devices,
tissue engineering.
Tissue engineering;
Food 3D printing
Bone tissue engineering
Tissue engineering,
fabrication of complex
and clinically sized soft
tissues;
Tissue engineering,
heart valves
replacement;
Myoregenerative
application;
Bone tissue engineering;
Achievements/comments
packaging, textiles, health care
products, and furniture;
Tip clogging is challenge,
mechanical properties of the
printed structures still need to be
optimized.
Evaporation of acetone limited the
manufacturing rate.
Temporary integration of
methylcellulose offers better
printability while keeping the
advantages of low-concentrated
alginate bioink for cell embedding.
Dispersion and interfacial adhesion
between the cellulose and the PLA
were improved with low ratio of
modified cellulose.
– DWoC Ali (2015)
– Xu et al. (2018)
Biocompatibility of the scaffolds
needs to be studied in the future;
Starch working as thickening /
gelling agent, rheological modifier,
and carbohydrate source.
Post-processing, surface
functionalization / coating,
incorporation of (in-)organic
components to tune the
biochemical, material-cellular
responds, mechanical, and
morphological properties of PLA-
based scaffolds.
Effect of bioink properties (e.g.
oxidization degree, viscosity, and
density) on the printability,
structural stability, and
degradability were investigated.
Diffusion of crosslinker Ca2+ may
have negative effect on Ca2+
sensitive cell types;
Three crosslinking stages allow for
tuning the bioink printability,
References
J. Liu et al.
Pattinson and Hart (2017)
Schütz et al. (2017)
Murphy and Collins
(2016)
Lam et al. (2002), Lille
et al. (2018), Liu, Zhang,
Bhandari, Yang (2017),
Schutyser et al. (2018),
Yang et al. (2018)
Kao et al. (2015), Park
et al. (1998), Serra,
Planell et al. (2013),
Senatov et al. (2016),
Wang et al. (2016) Zhang
et al. (2016)
Bendtsen et al. (2017),
Chung et al. (2013) Duan
et al. (2013), Daly et al.
(2016), Diogo et al.
(2014), Gudapati, Yan,
Huang, and Chrisey
(2014),
Jia et al. (2014), Tabriz,
Hermida, Leslie, and Shu
(2015), Wu et al. (2016)
(continued on next page)
Carbohydrate Polymers 207 (2019) 297–316
 Table 1 (continued)
Biobased printing Printing/solidification approach
materials
Matrix-assisted pulsed-laser
evaporation direct-writing,
crosslinking with 2% (w/v) CaCl2;
3D bioprinter, modified from a Fab@
Home RP platform, crosslinked in
300 mM CaCl2;
Extrusion-based bioprinting,
crosslinked with 2% w/v CaCl2;
3D bioprinting;
Rapid prototyping (Fab@home)
304
Agarose/collagen 3D drop-on-demand printing with the
supporting effect of perfluorocarbon
(cooled down to 10 °C to accelerate
the agarose gelation)
Agar/alginate Modified extrusion-based 3D printing,
crosslinking with 0.5 M CaCl2 and UV
irradiation
Agarose Custom-made extrusion-based 3D
printing in a hydrophobic high-
density fluid (C12F27N2);
Extrusion-based bioprinting;
Ink formulation
of alginate (1, 2, 4% w/v) gelatin (10% w/v),
4:1;
Mouse calvaria 3T3-E1 cells-laden alginate-
polyvinyl-alcohol-hydroxyapatite hydrogel
bioink;
Arg-Gly-Asp adhesion peptides incorporated
and gamma-irradiated alginate bioink,
reinforced with polycaprolactone fibers β-
tricalcium phosphate/alginate hybrid
materials;
Human corneal epithelial cells-laden
collagen/gelatin/alginate hydrogel bioink
Agarose (0.25-1.5%) and type I collagen
(0.2%)
Agar, alginate, acrylamide, N,N’-
methylenebis(acrylamide), photo-initiator
Human mesenchymal stem cells-laden
agarose hydrogel (1.5%);
Smooth muscle cells and fibroblasts-laden
multicellular spheroids or cylinders
concomitantly were printed with agarose
rods template followed by post fusion to
form vascular tubes;
Hela cells-laden agarose hydrogel (1, 1.25,
1.4%)
Printed structure
porous, cylindrical scaffolds;
Vertebrae constructs;
Rectangular construct
Columns structure (2-3 cm)
Dogbone and meniscus
Vascular bifurcation and
cylinder structure;
Vascular tubular grafts;
Cylinder, box, and ear
structure.
Potential applications Achievements/comments References
J. Liu et al.
mechanical properties, and long-
term structural stability;
Cell viability was found to be
affected by the alginate gelation
processes, including alginate
concentration, gelation time, and
laser fluence. Process-induced cell
injury arises from mechanical
stress, thermal effect of laser
fluence, and chemical effect of
Ca2+;
Mechanically robust living tri-
leaflet heart valves were bioprinted
by encapsulating VIC and SMS
cells;
Pre-crosslinked alginate ink was
not suitable for printing due to low
resolution and fluid-like properties
of the printed scaffolds;
Further in vitro studies of cells
differentiation to regenerate new
bone are needed;
Complex solid organs can be
fabricated by bioprinting
precursors that have the capacity to
mature into their adult
counterparts over time in vivo;
Further surface functionalization to
facilitate bioadhesion and to
improve mechanical properties
using different polymers or
ceramics are needed;
The degradation profile of the
bioprinted constructs can be tuned
by altering the ratio of sodium
citrate/sodium alginate,
Drug discovery Impact of hydrogel structure, Köpf et al. (2016)
stiffness, and composition on cell
morphology and possibility of
mechanical reinforcement of the
blend hydrogel should be further
investigated.
Load-bearing tissue – Wei et al. (2015)
substitutes
Tissue engineering and Promising approach allows for Duarte Campos et al.
regenerative medicine; fabrication of compositionally and (2013), Norotte et al.
Tissue architecturally intricate tissue; (2009), Navarro and
fabrication Higher resolution is needed to print Garcia (2016), Wu et al.
complex structure. (2017)
(continued on next page)
Carbohydrate Polymers 207 (2019) 297–316
J. Liu et al. Carbohydrate Polymers 207 (2019) 297–316

hydrogels with shear thinning behavior and high zero shear viscosity
have been tested as inks for 3D bioprinting. Rees et al. (2015) prepared

Demirtaş et al. (2017)

Almeida et al. (2014),

(2017), Morris et al.

Elviri, Foresti et al.
the CNF hydrogels with TEMPO-mediated oxidation and a combination
of carboxymethylation and periodate oxidation and used to print 3D
porous structures for wound dressing application. Both CNF-based inks
References

were found to inhibit bacterial growth, suggesting the potential appli-

(2016),
chemistry, topography and scaffold
Wrinkle formation and its impact
cation as wound dressing materials. The CNF prepared from TEMPO-
mediated oxidation failed to print constructs with acceptable resolution
and desired tracks due to the limited low consistency (0.95%) but re-

The macrophage responses were

found to be affected by material
scaffold biodegradation kineties

performance in mechanical and

Chitosan-based hydrogel were latively high viscosity. The one prepared by carboxymethylation and
on cell growth, as well as the

cellular activities supporting.

periodate oxidation was suitable for being used as bioink in terms of
Achievements/comments

still need to investigate;

high consistency (3.9%) and appropriate rheological properties. The

found to have superior

printed 3D structures have fine tracks with open porosity and have the
potential to carry and release antimicrobial components for wound
dressing. Carboxymethylated CNF with high surface charge and higher
architecture;

consistency (2%) which holds the 3D shape after deposition has been
investigated as ink to print 3D structures (Håkansson et al., 2016). By
controlling the solidification process, e.g. air drying, air drying with
surfactants, solvent exchange before drying, and freeze drying, 3D
Potential applications

printed structures with desired mechanical, surface texture, and porous

structure can be obtained (Fig. 4A). Incorporation of functional in-
Soft tissue repair;
Tissue or organ

Cartilage tissue

gredients, e.g. conductive carbon nanotubes, offers additional func-

regeneration;

Engineering.
Bone tissue

tionality to the printed products. As shown in Fig. 4B, C, the conductive

repairing;

ink which composed of carbon nanotubes and CNF can be printed in the
CNF hydrogel matrix in different layers with fine resolution. After
drying, two over crossing conductive lines with decent electrical con-
orthogonal-diagonal double
Multi-layers scaffolds, thick

ductivity were separated by the insulation CNF layers, suggesting a

Orthogonal displaced and

potential for fabrication of sustainable commodities such as packaging,

Disk shaped hydrogel,
Multi-layers scaffolds;

textiles, biomedical devices, and furniture with conductive parts.

Printed structure

Pattinson and Hart (2017) demonstrated the manufacture of fully

layer scaffold;

1 mm x 6 mm

dense cellulose-based materials using cellulose acetate by 3D printing.

Ear scaffold;

The cellulose acetate has 80% of the surface hydroxyl groups sub-
stituted by acetate groups which effectively disrupted the hydrogen
film;

bonding network of native cellulose and made it possible to be dis-

solved in acetone with high consistency (25–35%). Solid cellulose
MC3T3-E1 pre-osteoblast cell laden chitosan
(2% w/v, in 0.1 M acetic acid) and chitosan-
and 1:15, and photoinitiator (Irgacure 819);
8% chitosan hydrogel (in an acidic mixture:

polyethylene glycol diacrylate at 1:5, 1:10,

40 vol. % acetic acid, 10 vol. % lactic acid,

Chitosan (6% w/v) and chitosan-raffinose

acetate structures with isotropic strength and high toughness were built
Photocurable resin consist of chitosan :

upon the evaporation of acetone. By incorporation of antimicrobial

agents, direct 3D printing of cellulose acetate-based objects with tai-
3% chitosan (in 2% acetic acid);

lored biochemical functionality (e.g. antimicrobial properties) can be

solution (in 2% acetic acid);

achieved, enabling customization of medical instruments in short time

hydroxyapatite hydrogels
and 3 wt. % citric acid);

(e.g. forceps with customized tips, Fig. 4D).

Methylcellulose has been utilized by Schötz et al. (2017) to enhance
Ink formulation

the temporary printability of a 3% alginate which has limited viscosity.

The addition of methylcellulose significantly enhanced the bioink
viscosity, enabling accurate and easy 3D bioplotting of constructs with
tailored architecture and of high shape fidelity, after which the me-
thylcellulose was released from the scaffolds during the following cul-
tivation. The embedded mesenchymal stem cells in the 3D printed
dried at 50 °C for 24 h, neutralized in
Extrusion-based 3D printing, vacuum

(Customized from a FDM), frozen on

the cooling substrate and gelation in

Extrusion-based bioprinting, thermal

methylcellulose-alginate scaffolds were found to maintain their differ-

Direct ink printing, in situ cross-
linking with NaOH (8% w/v) in
Printing/solidification approach

Stereolithography, cured using

entiation potential with high viability. The temporary integration of

crosslinking with the glycerol
a 1 M NaOH solution for 2 h;

Extrusion-based 3D printing

methylcellulose into the alginate-based bioink with low concentration

allowed the generation of scaffolds with high shape fidelity and stabi-
lity while keeping the advantages of low-concentrated alginate bioink
phosphate at 37 °C
KOH (8% w/v);

for cell embedding.

ethanol (70%);
405 nm laser;

A research team from Aalto University working within the project of

“Design Driven Value Chains in the World of Cellulose” studied 3D FDM
printing of thermoplastic cellulose derivatives (Ali, 2015). Printability
of the pure cellulose derivative was improved through plasticization
which reduced melt viscosity, improved the layer adhesion, and low-
ered glass transition temperature, allowing manufacture of a variety of
Table 1 (continued)

cellulose-based 3D structures. Similarly, within the same project, oxi-

Biobased printing

dized cellulose hydrogel, cellulose-based plastics, and pulp fiber com-

posites were studied for textile printing (Fig. 4E, F) (Kataja, 2015;
materials

Chitosan

Tenhunen et al., 2018). Structure with desired look or feel, e.g. hard or
soft, strong or brittle, stiff of flexible, porous or dense texture, can be
printed directly on substrates or fabrics or form self-standing structures

305
J. Liu et al.
and can find applications from medical science to personalized sports-
wear.
3.1.3. 3D printing of cellulose composites-based materials
Incorporation of other ingredients into the cellulose-based ink for-
mulations may significantly improve ink properties such as processa-
bility, printability, mechanics, and bioactivity (Guvendiren et al.,
2016). CNF hydrogels have ideal structural similarity to ECM and ex-
cellent rheological properties for 3D printing. However, the pure CNF
printed structures lack high shape fidelity (fine line resolution), suffi-
cient mechanical properties for handling during transplantation, and
long-term structure stability, limiting its application in the 3D printing
of complex scaffolds in different biomedical applications (Gatenholm
et al., 2016). Alginate also possesses shear thinning behavior at high
shear forces, but the low viscosity at zero shear rate makes it difficult to
print 3D constructs. Inks composed of CNF and alginate keep the shear
thinning behavior and high zero shear viscosity of CNF while the al-
ginate allows cross-link by divalent ions to maintain a long-term shape
fidelity and structural integrity after 3D printing.
Markstedt et al. (2015) optimized and evaluated the printability and
biocompatibility of this composite ink. Anatomically shaped cartilage
structures, such as a human ear and sheep meniscus, were 3D printed
with high shape fidelity and stability (Fig. 5A–C). Human nasoseptal
chondrocytes were incorporated into the CNF-alginate composite ink
306
Carbohydrate Polymers 207 (2019) 297–316
Fig. 4. 3D printed structures using cellulose
derivatives. 3D printed and freeze-dried car-
boxymethylated CNF chair (A); Schematic
drawing and the printed carboxymethylated
CNF structure, where the black conductive
lines are clearly separated by the translucent
CNF (B); Images of the flexible electrical con-
ductive film after drying in air (C); Miniature
forceps with customized tips printed using
cellulose acetate containing antimicrobial dyes
(D); 3D printed cellulosic structure on fabrics
and multiple layers textiles (E, F). 3D printed
structures are adapted with permission from:
Håkansson et al. (2016)), Copyright (2016),
John Wiley and Sons; Pattinson and Hart
(2017), Copyright (2017), John Wiley and
Sons; 3D printed fabrics photos from VTT,
Finland.
for 3D bioprinting and the results suggested that the shear forces during
mixing and the cross-linking process could result in the decrease of cell
viability. Although the cell viability can be recovered after 7 days
culture, cells embedded in the structures (e.g. thickness exceeds 150-
200 μm) may gradually lose viability due to the limited diffusion
oxygen/gas, nutrients, growth factors, and waste-product (Ventola,
2014).
To overcome this issue, Martínez Ávila, Schwarz, Rotter, and
Gatenholm (2016) printed a chondrocyte-laden patient-specific auri-
cular construct with open porosity for oxygen, nutrients, and waste
diffusion (Fig. 5D). The bioprinted constructs showed an excellent
shape and size stability after bioprinting and long-term 3D culture and
the CNF-alginate bioink was found to support redifferentiation of
human chondrocytes, reestablishing and maintaining their chondro-
genic phenotype, suggesting the usefulness of the bioink for auricular
cartilage tissue engineering and many other biomedical applications.
Similarly, Nguyen et al. (2017) designed the human-derived in-
duced pluripotent stem cells (iPSCs) and irradiated human chon-
drocytes laden CNF-alginate/hyaluronic acid composite inks to mimic
the cartilaginous tissue for potential cartilage lesions treatment. In the
composite inks, the CNF was supposed to mimic the bulk collagen
matrix, alginate stimulates proteoglycans, and hyaluronic acid serves to
substitute the hyaluronic acid in native cartilage. Bioink of CNF-algi-
nate was found to maintain the pluripotency of the stem cell and to
J. Liu et al.
support the new generation of cartilaginous tissue with collagen ex-
pression and high cell density, suggesting the bioprinting of iPSCs with
CNF-alginate bioinks as a promising treatment to repair damaged car-
tilage.
Alginate sulfate with the potential to supports chondrocyte pheno-
type has also been incorporated into CNF hydrogel to formulate bioinks
for cartilage bioprinting (Müller, Öztürk, Arlov, Gatenholm, & Zenobi-
Wong, 2016). The composite bioink was found to promote bovine
chondrocytes spreading, proliferation, and collagen II synthesis. How-
ever, the bioprinting process significantly compromised cell prolifera-
tion, especially in the case that uses nozzles and valves with a small
diameter and high extrusion pressure and stress.
Currently, the CNF-alginate composite ink formulation has been
successfully commercialized with the brand name of CELLINK® and has
been evaluated in vitro and in vivo with human chondrocytes, human
dermal fibroblasts and keratinocytes, neural cells, mesenchymal stem
cells derived from bone marrow, and adipose tissue and iPSC cells de-
rived from chondrocytes (Gatenholm et al., 2016). For example,
Henriksson, Gatenholm, and Hagg (2017) bioprinted the living adipo-
cytes-laden CELLINK® bioink and a bioink composed of nanocellulose
and hyaluronic acid (CELLINK-H) for 3D bioprinting in adipose tissue
engineering. The adipocytes laden in 3D printed structures, especially
the CELLINK-H, produced better adipogenic differentiation and more
mature cell phenotype with larger lipid droplets than conventional 2D
culture system, suggesting a promising method for adipose tissue en-
gineering. The clinical study has recently been conducted by trans-
planting the bioprinted cell-laden CELLINK® bioink scaffold in a sub-
cutaneous pocket of mice (Möller et al., 2017) (Fig. 5E). The
histological, immunohistochemical, and mechanical analysis suggested
that the 3D bioprinted scaffolds have excellent structural integrity,
shape fidelity, and good mechanical properties after 60 days of im-
plantation and the scaffolds can result in cartilage synthesis, suggesting
the potential application of the CELLINK® bioinks in 3D bioprinting
cartilage tissue for application in reconstructive surgery.
307
Carbohydrate Polymers 207 (2019) 297–316
Fig. 5. 3D printed human ear (A and D) and
sheep meniscus (B and C) with CNF-alginate
bioink; Photograph of an hNC-laden scaffold
after 14 days of implantation (E). Adapted with
permission from Markstedt et al. (2015),
Copyright (2015), American Chemical Society;
Martínez Ávila et al. (2016), Copyright (2016),
Elsevier; Möller et al. (2017), Copyright
(2017), Wolters Kluwer Health.
3.1.4. 3D printing of hemicelluloses-based materials
Hemicelluloses, which mainly include xylans, glucomannans, ara-
binans, galactans, and glucans, are a type of heterogeneous poly-
saccharides and are widely distributed in biomass. Hemicelluloses have
long been studied and widely used in different areas, such as food and
feed, medicine and pharmaceutics, and papermaking due to their bio-
compatibility, biodegradability, nontoxicity, and some specific ther-
apeutic activities (Liu, Willför et al., 2015). However, utilization of
hemicelluloses either in native or their functionalized products as
feedstocks for 3D printing has rarely been studied.
Recently, a spruce wood hemicellulose (O-acetyl galactogluco-
mannan, GGM) was utilized to partially replace the synthetic PLA as
feedstock in 3D FDM printing (Xu et al., 2018). The blends of hemi-
celluloses and PLA with a varied ratio up to 25% of GGM were evenly
mixed with a solvent casting approach and were extruded into filaments
by hot melt extrusion. 3D scaffold prototypes were successfully printed
from the composite filaments by FDM 3D printing (Fig. 3). As a pioneer
exploration, this study demonstrated the feasibility of applying bior-
enewable hemicelluloses as a novel material candidate for FDM 3D
printing, which has explored a new route to utilize hemicellulose-based
biopolymer in 3D printing for versatile applications in, but not limited
to, biomedical devices.
By mimicking the hemicelluloses’ natural affinity to cellulose,
Markstedt, Escalante, Toriz, and Gatenholm (2017) mixed a tyramine
substituted xylan with the CNF to introduce cross-linking property of
the all-wood-based inks for 3D printing. The tyramine substitution de-
gree of the xylan-tyramine and the mixture ratio were found to influ-
ence the printability and cross-linking density of the all-wood-based
inks, and the swelling properties of the printed structure, opening the
opportunity to tune the mechanical and structural properties of the
printed object and might even transfer into 4D printing.
J. Liu et al. Carbohydrate Polymers 207 (2019) 297–316

(caption on next page)

308
J. Liu et al. Carbohydrate Polymers 207 (2019) 297–316

Fig. 6. Molecular structures of starch and PLA and their representative 3D printed structures (A); Molecular structures of alginate and agarose and their re-
presentative 3D printed structures (B); Molecular structures of chitin and chitosan and the representative 3D printed structures (C); 3D printed structures are adapted
with permission from: Lam et al. (2002), Copyright (2002), Elsevier; Schutyser et al. (2018), Copyright (2017), Elsevier; Liu, Zhang, Bhandari, Yang (2017),
Copyright (2017), Elsevier; Yang et al. (2018), Copyright (2018), Elsevier; Wang et al. (2016), Copyright (2016), Elsevier; Senatov et al. (2016), Copyright (2016),
Elsevier; Serra, Mateos-Timoneda et al. (2013), Copyright (2013), Taylor & Francis; Liberski (2016) HBKU Press; Duarte Campos et al. (2013), Copyright (2013), IOP
Publishing; Norotte et al. (2009)), Copyright (2009), Elsevier; Wei et al. (2015), Copyright (2015), Royal Society of Chemistry; Hong et al. (2015), Copyright (2015),
John Wiley and Sons; Chavanne et al. (2013), Copyright (2013), Walter de Gruyter; Li et al. (2009), Copyright (2009), SAGE Publications; Wu (2016), Copyright
(2016), Elsevier; Morris et al. (2016), Copyright (2016), Springer.

3.2. 3D printing of starch-based materials
Starch is another type of abundant polysaccharide produced by
higher plants as energy storage and is composed of the linear amylose
and highly branched amylopectin with structures of α-(1→4) linked
glucan and the α-(1→4) linked glucan with α-(1→6) branch linkages,
respectively (Fraser-Reid, Tatsuta, & Thiem, 2008) (Fig. 6A). Utilization
of starch or starch-based polymers, e.g. thermoplastic starch and PLA,
as feedstocks in 3D printing technologies for a variety of application
draw increasing interest from both academic research and industry
application owing to its renewability, biodegradability, biocompat-
ibility, and high abundance in nature (Davachi & Kaffashi, 2015; Li
et al., 2014; Zeng, Li, & Du, 2015).
A three-powder blend ink consisted of 50 wt.% corn starch 30 wt.%
dextran and 20 wt.% gelatin and water-based binders were adapted for
3D printing of porous scaffolds for tissue engineering application (Lam,
Mo, Teoh, & Hutmacher, 2002). After 3D printing, post-processing by
heat treatment (dried at 100 °C for 1 h) was applied to sinter the three-
blend powdered particles together via necking connections, enhancing
the strength of the scaffolds and also the water resistance. Although the
fabricated porous scaffolds which consisted of natural polymers and
water-based binder showed potential in tissue engineering, further
biocompatibility study is needed.
In 3D food printing, starch is commonly utilized as a thickening/
gelling agent or rheological modifier, and also serves as an important
carbohydrate source. Incorporation of starch into the ink formulation
improves the ink printability by offering the ink with shear thinning
behavior and also the shape stability of the printed structure. For ex-
ample, starch has been applied to facilitate the 3D printing of sodium
caseinate (Schutyser, Houlder, de Wit, Buijsse, & Alting, 2018), mashed
potatoes (Liu, Zhang, Bhandari, & Yang, 2017), lemon juice gel (Yang,
Zhang, Bhandari, & Liu, 2018), and a protein and fiber-rich food ma-
terials, (Lille et al., 2018) by working as thickening/gelling agent.
Similar to cellulose, the structure of starch also has abundant hy-
droxyl groups, (Fig. 6A) offering numerical chemical modification/
functionalization possibilities to produce starch derivatives or starch-
based polymers or plastics for 3D printing (BeMiller & Whistler, 2009).
For instance, a thermoplastic starch (TPS) / acrylonitrile-butadiene-
styrene (ABS) copolymers was prepared by using a compatibilizer
(styrene maleic anhydride) to generate hydrogen bonds as well as
strong van der Waals force between TPS and ABS and were subjected to
filament extrusion and FDM 3D printing. The results revealed that the
TPS/ABS filaments and thereof printed 3D structures have superior
mechanical properties and thermal resistance than that of commercial
ABS, suggesting that the potential of using biomass polymeric materials
and their derivatives with excellent 3D printing processibility and
physical performance would be highly promising in the future (Kuo
et al., 2016).
As shown in Fig. 6A, through fermentation with micro-organisms
and polymerization processes, polylactic acid (PLA) can be produced
from starch in a sustainable and a green approach. Owing to a variety of
benefits, including biocompability, nontoxicity, biodegradability, ease
of processability, low cost, excellent mechanics, and the green feature
of its synthesis routes from renewable resources, PLA makes up the
majority of the FDM 3D printing feedstock and has drawing increasing
interest from biomedical application, such as scaffolds, implants,
prostheses, drug-based delivery systems, and anatomical models fabri-
cation (Davachi & Kaffashi, 2015; Guvendiren et al., 2016; Modjarrad &
Ebnesajjad, 2014; Pilla, 2011; Saini, Arora, & Kumar, 2016; Tyler,
Gullotti, Mangraviti, Utsuki, & Brem, 2016). Depend on the ratio of
PLLA and PDLA, the mechanical performance and crystalline structure
of the polymers can be tailored for specific requirements of different
biomedical applications. For example, sutures and orthopedic devices
which need high mechanical strength and toughness can be fabricated
with a high ratio of PLLA, while drug delivery systems that require a
porous and monophasic matrix can be produced with the amorphous
PDLA (Shah Mohammadi, Bureau, & Nazhat, 2014).
Although the abovementioned benefits of PLA render the board
applications in biomedical and pharmaceutical areas, some dis-
advantages of PLA, such as the hydrophobic nature, low ultimate
elongation strain, lack of cell motif sites, small particle and the acidic
byproduct of PLA degradation which induce foreign-body inflammatory
reactions, may cause clinical complications and limited its use in bio-
medicine (Suganuma & Alexander, 1993). Therefore, increasing efforts
have been carried out to enhance the hydrophilic properties, to increase
the cell motif sites, to introduce bioactivity, to improve the ultimate
elongation strain, and to address the formation of acidic biodegradation
products (Manavitehrani et al., 2016; Ulery, Nair, & Laurencin, 2011).
For example, Wang et al. (2016) printed the PLA-based scaffolds and
treated with a cold atmospheric plasma (CAP) modification for en-
hancing hydrophilicity and cell motif sites. The ends of the PLA chains
(−CH3) on the surface were reacted with the reactive oxygen species
(peroxides, superoxide, hydroxyl radical, and atomic oxygen) and were
converted to hydrophilic groups, e.g. −CH2OH, −CHO, −COOH.
Meanwhile, the CAP treatment raised the surface temperature of the
PLA to ca. 40 °C, which partially molt and reform the polymer, allowing
for a conversion from micro-scale to nano-scale surface features. Results
showed that the enhanced surface hydrophilicity and nano-scale
roughness by CAP surface modification significantly promoted both
osteoblast (bone forming cells) and mesenchymal stem cell attachment
and proliferation, suggesting promising application in bone tissue en-
gineering (Wang et al., 2016).
Except for the physical treatment, surface functionalization with
bioactive molecules is another approach for improving biomaterials
bioactivity. For instance, Kao et al. (2015) functionalized 3D printed
PLA scaffolds via a mussel inspired surface coating with polydopamine
to accelerate protein adsorption and cell cycle of the human adipose-
derived stem cells. Similarly, surface coating of PLA scaffolds by phy-
sical sorption and covalently bonding of collagen and polymers (poly-
ethyleneoxide-polypropyleneoxide copolymers), or by incorporation of
bioactive glass have also been adapted to improve scaffolds bioactivity
and to tune cell response (Park, Ben, & Griffith, 1998; Serra, Mateos-
Timoneda, Planell, & Navarro, 2013; Serra, Planell, & Navarro, 2013).
The surface coated or modified PLA scaffolds are demonstrated to
regulate cell organization, adhesion, proliferation, and to induce os-
teogenesis and angiogenesis differentiation, providing a very promising
tool to regulate stem cell behavior, and may serve as an effective stem
cell delivery carrier for bone tissue engineering (Kao et al., 2015; Lin &
Fu, 2016).
Modification or functionalization of PLA to tune the mechanical
performance of the 3D printed PLA-based scaffolds also play a key role
in its biomedical application. Senatov et al. (2016) designed and

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fabricated a PLA-based porous scaffold with a shape memory effect by
FDM 3D printing for potential application as a self-fitting implant in
bone defect replacement. PLA which serves as bioresorbable matrix and
the bioactive filler hydroxyapatite (HA) powder (15 wt.%) were mixed
in a screw extruder and the PLA/HA composite filaments were extruded
for FDM 3D printing. The 3D printed PLA-based porous scaffolds were
shown to have the shape memory effect after the heat activation which
changed the polymer chain mobility. The scaffolds were found to be
able to withstand up to three compression-heating-compression cycles
without delamination. However, the higher activation temperature
(70 °C) for the shape memory effect than body temperature is an ob-
stacle for the application and therefore further study to lower the ac-
tivation temperature is needed (Senatov et al., 2016). Similarly, Zhang
et al. (2016) prepared a PLA/HA (15 wt.%) composite scaffolds with a
pore size of 500 μm and 60% porosity by a mini-deposition system
(FDM) (Jiang, Shi, Li, & Sun, 2012). Incorporation of HA can not only
enhance the mechanical performance of the scaffolds (Jiang et al.,
2012), but also find to offer the scaffolds with better biocompatibility,
biodegradability, and osteoinductive activity than the pure PLA scaffold
to enhance bone formation, showing potential application in bone
tissue engineering as promising candidate for bone defect repair (Zhang
et al., 2016).
3.3. 3D printing of algae-based materials
Algae-based materials, e.g. alginate, agarose, and carrageen which
extracted from brown and red algae, represent another group of natu-
rally-derived biopolymers from marine biomass for 3D printing inks
formulation, especially for 3D bioprinting (Axpe & Oyen, 2016).
Alginate is one of the most widely explored seaweed anionic poly-
saccharides composed of β-(1→4)-linked D-mannuronic acid (M block)
and α-L-guluronic acid (G block) units arranged with varying propor-
tion of GG, MG, and GM blocks (Fig. 6B) (Liu, Willför et al., 2015). It
has been recognized as the most commonly employed material as
bioink formulation in 3D bioprinting for a variety of biomedical and
pharmaceutical applications, such as wound healing, cartilage repair,
bone regeneration and drug delivery, owning to the benefits of non-
toxicity, biocompatibility, biodegradability, non-antigenicity, and ease
and mild of gelation (Axpe & Oyen, 2016; Chimene, Lennox, Kaunas, &
Gaharwar, 2016; Duan, Hockaday, Kang, & Butcher, 2013; Lee &
Mooney, 2012; Liberski, 2016; Sun & Tan, 2013). By mixing with
multivalent cations, e.g. Ca2+, alginate is ionically crosslinked to form
a hydrogel, offering an ECM mimicking environment for cells in-
corporation and survival, good printability, structural integrity and
mechanical stiffness. By adjusting or utilize alginate with different G/M
ratio, molar mass, solid content, as well as cell density, the rheological,
mechanical, the macro- and micro- structural properties of the alginate-
based bioink can be tuned to fit the requirements of different bio-
printing methodologies and different biomedical applications (Fig. 6B)
(Axpe & Oyen, 2016; Grigore, Sarker, Fabry, Boccaccini, & Detsch,
2014; Liberski, 2016; Luo et al., 2015).
However, some undesirable features, including poor long-term
structural integrity and mechanical properties, slow and uncontrolled
degradation kinetics, and the bioinert property (non-cell-adhesion by
itself), should be carefully considered in the design and development of
alginate-based bioink for bioprinting (Chung et al., 2013). For instance,
the poor mechanical performance could be addressed by combining
ionic and covalent crosslinking (Bakarich, Panhuis, Beirne, Wallace, &
Spinks, 2013; Duan, Kapetanovic, Hockaday, & Butcher, 2014; Grigore
et al., 2014; Kesti et al., 2015; Kong, Kaigler, Kim, & Mooney, 2004;
Rutz, Hyland, Jakus, Burghardt, & Shah, 2015), by incorporation of
other component such as hydroxyapatite (Bendtsen, Quinnell, & Wei,
2017; Wöst, Godla, Möller, & Hofmann, 2014), polycaprolactone (Daly
et al., 2016; Shim, Lee, Kim, & Cho, 2012), β-tricalcium phosphate
(Diogo, Gaspar, Serra, Fradique, & Correia, 2014), and nanocellulose
(Markstedt et al., 2015; Martínez Ávila et al., 2016; Möller et al., 2017),
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Carbohydrate Polymers 207 (2019) 297–316
and by assisting deposition of a sacrificial layers (e.g. PEG) that can be
removed after printing (Armstrong, Burke, Carter, Davis, & Perriman,
2016; Lee et al., 2014). The slow degradation kinetics of native alginate
can be addressed by oxidation with sodium peroxide or periodate
(Boontheekul, Kong, & Mooney, 2005; Grigore et al., 2014; Jia et al.,
2014; Kong et al., 2004), by controlling the alginate molar mass and
distribution (Boontheekul et al., 2005; Kong et al., 2004), by enzyme
assisted degradation (e.g. alginate lyase) (Wong, Preston, & Schiller,
2000), or by incubation with sodium citrate that accelerates the dis-
solve of alginate hydrogel by chelating calcium ions from the CaCl2
cross-linked alginate hydrogel (Wu et al., 2016). The bioinert property
of native alginate can be addressed by conjugation of cell attachment
ligands (e.g. peptide sequence Arg-Gly-Asp, i.e. RGD), or by in-
corporation of other biomacromolecules, such as fibrin, collagens, ge-
latin, chitosan, hyaluronic acid, avidin protein, and various growth
factors to offer desired bioactivities (Abhay et al., 2013; Chung et al.,
2013; Daly et al., 2016; Grigore et al., 2014; Jia et al., 2014; Kundu,
Shim, Jang, Kim, & Cho, 2015; Leppiniemi et al., 2017).
Agar and its purified agarose are galactose-based polysaccharides
derived from red algae and seaweed such as Gracilaria and Gelidium.
Agarose is a linear polysaccharide composed of alternating (1→4)-
linked (3,6)-anhydro-α-L-galactose and (1→3)-linked β-D-galactose
(Fig. 6B), while agar is a mixture of the predominant agarose and the
agaro-pectin that composed of partially sulfated (1→3)-linked D-ga-
lactose (Serwer, 1983; Stephen, Phillips, & Williams, 2006). These ga-
lactose-based polysaccharides, especially the agarose, have proven
suitable for bioprinting owning to the cytocompatibility, stable me-
chanical properties, and mild temperature dependent gelling condition
with the starting gelling temperature of 37 °C and fully crosslinking at
32.7 °C (Duarte Campos et al., 2013; Ferris, Gilmore, Wallace, & in het
Panhuis, 2013; Malda et al., 2013).
Different cell lines have been encapsulated into the agar, agarose,
and their composite hydrogel with other polymers such as alginate,
collagen, matrigel, and chitosan as bioinks in bioprinting for potential
application in tissue engineering, regenerative medicine, and drug
discovery (Duarte Campos et al., 2013; Köpf, Campos, Blaeser, Sen, &
Fischer, 2016; Landers, Hubner, Schmelzeisen, & Mulhaupt, 2002;
Landers, Pfister et al., 2002; Maher, Keatch, Donnelly, Mackay, &
Paxton, 2009; Navarro & Garcia, 2016; Norotte, Marga, Niklason, &
Forgacs, 2009; Tan et al., 2014; Wei et al., 2015) (Fig. 6B).
3.4. 3D printing of chitosan-based materials
Chitosan, a cationic polysaccharide, comprises of β-(1→4)-linked N-
acetyl-D-glucosamine and deacetylated D-glucosamine units (Fig. 6C). It
is the deacetylated form of chitin that naturally exists in exoskeletons of
crustaceans (crab, shrimp shells, and insects), as well as the cell wall of
fungi and yeast, which is the second richest natural polymer in nature
after cellulose (Dutta, 2016; Kumar, Muzzarelli, Muzzarelli, Sashiwa, &
Domb, 2004; Rinaudo, 2006). Chitosan-based biomaterials with unique
advantages have drawn increasing attention for application in medical
and pharmaceutical areas, such as tissue engineering, drug delivery,
and wound healing, owing to their biocompatibility, bioresorbability,
biodegradability, antimicrobial activity, mucoadhesivity, and low
toxicity, as well as natural abundance (Dutta, 2016; Elviri, Bianchera,
Bergonzi, & Bettini, 2017).
Generally, chitosan is soluble in acidic condition, e.g. 2% acetic
acid, and the amine groups in chitosan are protonated to confer the
poly-cationic behavior. The chitosan chains expand into a semi-rigid
rod conformation due to ionic repulsion between the charged groups
(NH3+) and thus the chitosan ink exhibits shear thinning behavior
which is beneficial for the extrusion-based 3D printing (Wu, Maire,
Lerouge, Therriault, & Heuzey, 2017). Chitosan or chitosan-based
composites in the form of hydrogel or paste, filaments or strip, have
been applied in a variety of 3D printing technologies for potential bone
tissue engineering, cartilage tissue regeneration, and drug screening
J. Liu et al.
(Fig. 6C). These printing approaches including: FDM (Wu, 2016), ste-
reolithography (Morris, Nimbalkar, Younesi, McClellan, & Akkus,
2016), and different nozzle extrusion-based 3D printing technologies
such as double-nozzle assembling (Li et al., 2009), rapid prototyping
robotic dispensing (Ang et al., 2002), direct-printing (Almeida et al.,
2014), and low temperature manufacturing (Elviri, Foresti et al., 2017),
However, the poor mechanical resistance and degradability in
physiological conditions, as well as the acidic dissolution made it dif-
ficult to incorporate living cells into the chitosan-based inks in bio-
printing for biomedical applications. Neutralization and gelation in
alkaline condition (Almeida et al., 2014; Demirtaş, Irmak, &
Gömöşderelioğlu, 2017; Elviri, Foresti et al., 2017; Wu et al., 2017),
derivatization, crosslinking, or a combination with other polymers, are
required prior to a cell seeding or implantation (Chavanne et al., 2013;
Liu, Chang, & Lin, 2015; Pandey, Singh, Momin, & Bhavsar, 2017; Yang
et al., 2016). For instance, hydroxyapatite, pectin, and genipin have
been incorporated into chitosan for mechanical reinforcement of
chiton-based inks or 3D printed scaffolds in bone tissue engineering
(Ang et al., 2002; Chavanne et al., 2013; Demirtaş et al., 2017; Liu,
Chang et al., 2015). Combination with other natural or synthetic
polymers, such as alginate, gelatin, fibrinogen, laminin, and thermo-
plastics, would potentially offers many opportunities to overcome these
challenges, and may allow to introduce some desired properties (Li
et al., 2009; Yan et al., 2005; Yang et al., 2016; Zhu, Li, Guan, Schreyer,
& Chen, 2010).
4. Current challenges and Strategical Roadmap
Despite the remarkable achievements having been reported for a
variety of 3D printing technologies in the past decade, which have also
expanded their advances or progresses in many types of material ex-
plorations and improvements, the feedstock advances, no doubt, remain
as a key and unique foundation for a large-scale application with 3D
printing technologies in many promising areas. As a matter of fact,
some challenges with respect to the material printability, functionality,
and safety (biosafety and environmental safety) still need to be fully
addressed both including therapeutic and nontherapeutic applications.
Particularly, it would be noteworthy that our attention during devel-
oping biopolymers as 3D printing feedstocks should be firstly put on
those challenges regarding their specific requirements for a 3D printing
method as well as a targeted application. Therefore, in future, more
efforts are truly required to make by following a biopolymer-based inks
development strategical roadmap, as shown in Fig. 7, in order to meet
numerous interdependent and technical requirements of different target
application, including those that lead to an optimal printing, superior
structural and functional outcomes by tuning the chemical, physical,
and biological properties of those potential and promising natural-de-
rived biopolymers (Jakus, Rutz, & Shah, 2016).
Challenges in the 3D printing of biopolymers applied in medical
area remain a large requirement to improve their material defects and
properties, i.e. printability, mechanical properties, biocompatibility,
tissue biomimicry, degradation kinetics, and safe degradation by-
products (Fig. 2A). The inherent physic-chemical properties of some
biopolymers, e.g. infusibility and insolubility in common solvents,
certainly pose the intractable challenges in the 3D printing process. To
address these issues, adapting or modifying commercial printers,
modifying natural-based biopolymers, developing novel solvents sys-
tems, incorporating other functional or bioactive polymers, as well as
advancing different post-processing technologies (such as surface
coating, and plasma radiation), should be put on our research agenda
with a strategical roadmap identified for their relative importance and
interdependence (Fig. 7) (Chia & Wu, 2015; Melchels et al., 2012).
Besides, blending different types of biopolymers aiming for a compli-
mentary advantage is another alternative approach or strategy to for-
mulate composite inks with favorable processability, printability, me-
chanics, and bioactivities. However, biodegradation discrepant of
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Carbohydrate Polymers 207 (2019) 297–316
different biopolymers may bring a challenge with respect to its struc-
tural replacement by cell-secreted ECM. Therefore, the balance between
the composite ink properties, and the resulted structural and functional
changes of the printed objects should be carefully considered
(Guvendiren et al., 2016; Köpf et al., 2016; Ning & Chen, 2017). In
addition, one key challenge for 3D printing biopolymers in biomedical
application, especially in tissue engineering, is the tissue biomimicry.
Manipulation of multiple biopolymers and cell types to print vascu-
larized and metabolically active thick tissues, such as, kidney, heart,
lung, and liver tissues, that can reproduce a complex architecture and
composition of natural tissue, is still an essential challenge in tissue
engineering (Ning & Chen, 2017; Novosel, Kleinhans, & Kluger, 2011;
Ventola, 2014). To date, proof-of-concept evaluations towards the 3D
printing of natural-derived biopolymers for a particular biomedical
application have been successfully demonstrated in a variety of mate-
rial forms, including beads, filaments, fibers, channels, sheets, rolls,
grids, and porous 3D constructs that mimic the tissue components.
However, these printed structures are often avascular (lacks blood
vessels), aneural (no neurons and nerves), and alymphatic (no lym-
phatic system). Direct or indirect extrusion-based bio-printing, micro-
fluidic and bioreactor techniques, have been developed to fabricate
micro or macro-channels to form vasculatures. However, there is still a
great deal of work to cope with regarding this critical limitation before
printing a functional tissue (Ning & Chen, 2017; Novosel et al., 2011;
Ventola, 2014; Zhang, Fisher et al., 2015). Another major challenge is
the limited capabilities of current 3D printers to process natural-derived
biopolymers for various biomedical applications. Processing speed and
resolution still lag behind the designed optimal levels in many cases.
For instance, angiogenesis guiding in an expected path requires precise
deposition of channels in designated regions for further vascularization
in bioprinting for tissue engineering application. Thus, 3D printers
capable of precise printing of multiple biopolymers and cell types with
high resolution, processing speed, and more precise robotic systems are
truly needed (Guvendiren et al., 2016).
3D food printing shows potential for customized food designs,
personalized nutrition, simplifying food supply chain, and broadening
of the available food materials but also poses challenges for the pro-
cessing of natural-derived biopolymers as 3D printing feedstock (Lin,
2015). Natural-derived biopolymers, such as starch, cellulose, hemi-
cellulose, alginate, agarose, and chitosan, can be potentially employed
as an ink formulation for 3D food printing. However, there is still a long
way for 3D food printing using biopolymers from the lab to kitchen.
Limited available printable biopolymers that are compatible with tra-
ditional food ingredients and conventional manufacturing processes
results in the high cost and infancy of the 3D food printing. Therefore,
3D food printing is currently mainly applied for customized food,
military and space food, elderly food, confectionery or sweets, instead
of for our daily food due to a high cost. For instance, such technology is
currently being considered by NASA to be used for printing of instant
food in spacecraft for longer duration space missions. However, with
key problems solved, 3D printed food will have the potential impact of
reducing global resource and providing alternative food source. The
main challenges of 3D food printing using biopolymers including: 1)
strict food safety safeguards of the biopolymers from difference sources;
2) appropriate rheological properties of biopolymers for processing and
printing and self-supporting; 3) acceptable printing precision and ac-
curacy; 4) manipulation of multiply biopolymers for personalized nu-
trition or flavors (Godoi et al., 2016; Liu, Zhang, Bhandari, Wang,
2017).
3D printing of apparel and textile products using bio-based mate-
rials holds advantages of quick product development, and personalized
design in a sustainable and renewable way, but also pose challenges to
designing, large scale production, post-processing, and most im-
portantly the safety concern. As for the apparel and textile products, 3D
printing shows high potential in an efficient and sustainable supply
chain through areas including reduced cost, lead time in production,
J. Liu et al. Carbohydrate Polymers 207 (2019) 297–316

Fig. 7. Strategical roadmap of the development of natural-derived biopolymers for 3D printing.

312
J. Liu et al.
and increased design possibility and efficiency. However, challenges
regarding less flexibility, insufficient mechanical properties, poor
washability, and poor integration of printed objects and fabrics prohi-
biting the technology from being a usual process in textile and clothing
production (Martens & Ehrmann, 2017). Apparel and textile products
require much more flexibility, resilience, and sufficient tensile strength
in accommodating to wearer’s comfort and body movement, which are
unfortunately hard to meet these performance requirements due to the
limited available printable polymers. Commonly used polymers, e.g.
PLA, nylon, or ABS, turns out to be too brittle for the desired fine
structures or too hard to be used in typical textile applications such as
garments. Combination of different types of fabrics and 3D printing
could be a good solution to develop innovative smart textiles by de-
position of functional polymers or intelligent materials onto textiles
without compromising on quality and flexibility of the fabric (Gao
et al., 2017; Hashemi Sanatgar, Campagne et al., 2017; Hashemi
Sanatgar, Cayla et al., 2017).
In summary, owning to the high abundance, low-cost, biocompat-
ibility and biodegradability, utilization of natural-derived biopolymers,
such as the lignocellulosic biomass, starch, algae, and chitosan-based
materials, either in native or in a functionalized product as feedstocks
for different 3D printing technologies offers a great deal of their po-
tentials and will in turn promotes an academic and industrial advance
in 3D printing materials development (Park et al., 2017). 3D printing of
natural-derived biopolymers in biomedical and pharmaceutical appli-
cations is considered as one of the most promising areas for its growth.
As a matter of fact, these potential applications mainly include, but not
limit to: 1) Bioprinting of vascularized and metabolically active tissues
that can reproduce a complex architecture with a unique composition of
natural tissues (such as, kidney, heart, lung, and liver tissues); 2) in situ
bioprinting of implants or living organs in the human body during
operations; 3) Personalized medicines with tailored dose, dose combi-
nation or even the active itself (Ventola, 2014).
Future research interests to expand the limited variety of available
natural-derived biopolymers as the novel 3D printing feedstock candi-
dates may include: 1) Development of novel solvent systems that are
cells-friendly and are capable of dissolving or dispersing natural-de-
rived biopolymers as inks formulations for different 3D printing; 2)
Manipulation of multiple biopolymers and incorporation of different
biomolecules as composite inks with user-defined and tunable proper-
ties, including desirable processability, printability, mechanics, bioac-
tivity, and biodegradability; 3) Modification or functionalization of
natural-derived biopolymers or the printed objects via biological, che-
mical, and physical approach to address the printability of the inks, or
to offer desired properties; 4) Incorporation of chemical or physical
stimuli responsive components into natural-derived biopolymers,
making the 3D printed objects programmable to external stimuli such
as pH, temperature, light, electric, and magnetic field, potentially
bringing forward current 3D printing to future 4D printing (Gao et al.,
2016; Wang, Lee, & Yeong, 2015).
5. Conclusions and future perspectives
3D printing has emerged as a revolutionary technology, promising
to transform the conventional products fabrication. However, limited
environmentally-friendly printing materials with a high quality of
printing performance reamins a major issue need to be overcome before
it can be widely adapted for products fabrication in different areas.
Natural-derived biopolymers, including lignocellulosic materials, sea-
weed materials, and materials from crustaceans exoskeletons (e.g. crab,
shrimp shells, and insects), represent the most abundant biobased and
renewable feedstocks for different 3D printing technologies.
Modification or combination with other ingredients to introduce or
improve the materials processability and products functionality will
indeed broaden the application areas of the natural-derived biopoly-
mers. Utilization of natural-derived biopolymers either in native or
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Carbohydrate Polymers 207 (2019) 297–316
their functionalized products as feedstocks for different 3D printing
technologies will be a future trend of 3D printing materials develop-
ment. Technical advances and the associated feasibility in developing
natural-derived biopolymers as feedstock formulations for a variety of
3D printing technologies have been confirmed and demonstrated in
recent years, at least at a scale of proof-of-concept level. However, there
is still a great deal of work waiting for us to cope with, such as in the
material processability, degradation, chemical, biological, and me-
chanical properties before achieving a full potential of biopolymers.
Once overcoming these challenges, 3D printing technology will no
doubt facilitate a rapid growing for the natural-derived biopolymer
applications in a variety of areas. Therefore, it can be predicted that the
future materials development in 3D printing will be gradually turned to
be a utilization of those natural-derived “green” feedstocks.
Acknowledgement
This work was supported by the National Natural Science
Foundation of China (31772529) and the Start-up Fund for Introduced
Scholar of Jiangsu University (4111370004).
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