0894 - Advanced Materials - 2022 - Saadi - Direct Ink Writing A 3d Printing Technology For Diverse Materials

Review
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Direct Ink Writing: A 3D Printing Technology for Diverse

Materials
M. A. S. R. Saadi, Alianna Maguire, Neethu T. Pottackal, Md Shajedul Hoque Thakur,
Maruf Md. Ikram, A. John Hart,* Pulickel M. Ajayan,* and Muhammad M. Rahman*
Manufacturing (AM) is the latest of these

Additive manufacturing (AM) has gained significant attention due to its ability strategies that have the potential to not
to drive technological development as a sustainable, flexible, and custom- only surpass traditional manufacturing
izable manufacturing scheme. Among the various AM techniques, direct limitations in efficiency and design but
also sustain the next generation of cul-
ink writing (DIW) has emerged as the most versatile 3D printing technique
tural and technological development.[1]
for the broadest range of materials. DIW allows printing of practically any The unique ability of AM is its design
material, as long as the precursor ink can be engineered to demonstrate freedom which can drive scientific and
appropriate rheological behavior. This technique acts as a unique pathway industrial advancements in the areas of
to introduce design freedom, multifunctionality, and stability simultaneously biology, chemistry, materials science, and
into its printed structures. Here, a comprehensive review of DIW of complex physics. Researchers have explored several
printing techniques within AM that allow
3D structures from various materials, including polymers, ceramics, glass,
the fabrication of materials at high speeds
cement, graphene, metals, and their combinations through multimaterial and precision over customizable build vol-
printing is presented. The review begins with an overview of the funda- umes. Of these, direct ink writing (DIW)
mentals of ink rheology, followed by an in-depth discussion of the various has emerged as one of the most versatile
methods to tailor the ink for DIW of different classes of materials. Then, the AM methods that enables a wide range of
materials to be utilized for creating com-
diverse applications of DIW ranging from electronics to food to biomedical
plex and/or periodic 3D structures.[2–4]
industries are discussed. Finally, the current challenges and limitations of this DIW is an extrusion-based AM tech-
technique are highlighted, followed by its prospects as a guideline toward nique that facilitates the fabrication of 3D
possible futuristic innovations. structures with intricate architectures and
compositions at the meso- and microscale.
In this process, the material as a viscoe-
1. Introduction lastic ink is extruded through a deposition nozzle in a layer-by-
layer fashion to build up scaffolds and other 3D geometry on
Beginning from the time of the early humans followed by the a computer-controlled translational stage.[5,6] After extrusion,
Copper age several millennia ago until the steel age of the 19th the 3D construct solidifies, generating a structure of desired
century, various tool making and manufacturing strategies features and properties.[2] Typically, DIW, also known as Robo-
have led to the advancement of human civilization. Additive casting, can be divided into two classes: droplet and continuous
ink extrusion.[5] The low cost, simplicity, and ability to combine
different materials in a single processing step in DIW have
M. A. S. R. Saadi, A. Maguire, N. T. Pottackal, M. S. H. Thakur, attracted a large number of research organizations and uni-
P. M. Ajayan, M. M. Rahman
Department of Materials Science and NanoEngineering versities worldwide to be involved in the state-of-the-art devel-
Rice University opment of the technique. First patented by Cesarano and Cal-
Houston, TX 77005, USA vert[7,8] at Sandia National Laboratory in 1997, DIW emerged as a
E-mail: ajayan@rice.edu; mr64@rice.edu printing technique for complex ceramic structures. Since then,
M. Md. Ikram the number of researchers using this technique has expanded
Department of Mechanical Engineering
Bangladesh University of Engineering and Technology
worldwide into a myriad of fields beyond structural ceramics.
Dhaka 1000, Bangladesh The published literature on DIW has also grown exponentially
A. J. Hart since 2006, as seen in the trend shown in Figure 1c, with major
Department of Mechanical Engineering engineering and scientific contributions coming from a wide
Massachusetts Institute of Technology range of disciplines.
Cambridge, MA 02139, USA DIW is distinct from other AM technologies in that it is not
E-mail: ajhart@mit.edu
limited by material class as long as the precursor ink exhibits
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202108855.
proper rheological behavior such as apparent viscosity, yield
stress under shear and compression, and viscoelastic proper-
DOI: 10.1002/adma.202108855 ties (i.e., loss and elastic moduli).[9,6] Therefore, this technique
Adv. Mater. 2022, 34, 2108855 2108855 (1 of 57) © 2022 Wiley-VCH GmbH
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Figure 1. DIW technology and ink rheology. a) Schematic process illustration of DIW. The technique has garnered significant attention because of its
ability to process the widest range of materials in fabricating complex multifunctional 3D structures. Inset shows one of the first experimental structures
developed by Cesarano in Sandia National Laboratory. Inset: Reproduced with permission.[8] Copyright 1997, Taylor & Francis. The structure was an
aluminum oxide “Thunderbird” made of 20 layers and sintered “crack-free” to 96% of theoretical density. b) Schematic showing the ideal rheological
response (storage modulus (G′)/loss modulus (G″) vs shear rate (σ)) of a printable ink and pressure-induced flow for a conventional ink that has bulk
non-Newtonian properties. Reproduced with permission.[6] Copyright 2020, Wiley-VCH. c) Recent trend in the number of publications on DIW. Data
from Web of Science (December 2021).
practically allows any ink to be effectively printed as a 3D struc- has led to extensive research in the advancement of 3D printing
ture with high-resolution patterning, architectural freedom, of polymers,[17–20] metals,[21–23] ceramics,[5,24,25] and even living
and distinct material properties intended. However, other AM materials[26–28] with tailored mechanical, electrical, thermal,
technologies such as fused filament fabrication (FFF), digital chemical, and biological properties. DIW, thus, offers powerful
light processing (DLP), stereolithography (SLA), and powder engineering design options for sophisticated and robust technol-
bed fusion (PBF) are very selective in the case of material ogies with relevance to biomedical devices,[29] artificial organs,[30]
printing. For instance, FFF is commonly used for printing tissue engineering,[31] energy storage platform,[32] optoelectronic
thermoplastic polymers, DLP and SLA techniques are suit- components,[33] metamaterials,[34] soft robotics,[35] electronics,[36]
able only for photopolymer resins, and PBF can print mostly sensors,[37] and even food printing.[38] Although the technique
metals, alloys, ceramics, and thermoplastic polymers. The has been mainly exploited in research labs for small-scale fab-
versatility of DIW is further emphasized through its unique rication and prototyping, it has the potential for easy and fast
ability to create novel multimaterial structures by separate and fabrication of industrial-level prototypes. Considering its versa-
simultaneous extrusion of different ink materials.[10] Thus, tility and continual development, DIW is expected to expand its
DIW’s potential to achieve multimaterial structures through impact and implementation in various industries in the future.
single-step processing streamlines overall manufacturing time, Here, we propose a comprehensive review on current
energy, cost, and waste without losing crucial material proper- advancements in DIW of various polymers, ceramics, glass,
ties. Further extending its capacity, DIW offers 4D printing as cement, graphene, metals, and their combinations via multi-
a promising technology for the development of shape-changing material printing. The review will provide an in-depth under-
smart materials that respond to external stimulation.[11,12] DIW, standing of the extrusion process, how ink composition is
as a manufacturing process, is also highly customizable as the developed for different classes of materials, or their combi-
print setup can be easily modified with interchangeable low- nation can be tailored to develop engineering structures with
cost components, including the three-axis platform, computer, desired properties and functionalities. Additionally, adaptation
and dispenser. The print conditions/setup can also be modified of DIW is assessed for applications ranging from electronics
via the incorporation of external stimulants such as magnetic and structural applications to biology and biomedical engi-
fields,[13] electromagnetic waves,[14] acoustic waves,[15] and heat neering. Finally, current challenges and future outlooks on
sources[16] which facilitate the fabrication of 3D structures with DIW are also addressed to understand potential avenues for
controlled microstructures. The richness in the potential of DIW forthcoming innovations.
2. Direct Ink Writing (DIW) Technology 102 and 106 mPa s range at a shear rate of approximately 0.1 s−1
to ensure printability of the inks.[20,32,41]
DIW is an extrusion-based layer-by-layer printing technique Once discharged from the printing head, the ink must rap-
that involves pressure-driven deposition of a viscoelastic ink idly transition from the shear-thinning fluid to a solid-like sub-
through a fine nozzle (process schematic shown in Figure 1a). stance to maintain its shape fidelity.[2] An important measure of
Typically, the DIW process includes three steps: 1) 3D modeling the ink’s ability to retain this shape fidelity is the ratio of loss
of structures generated by Computer-Aided-Design (CAD) soft- modulus (G″) to storage modulus (G′). Figure 1b shows the
ware, 2) 3D movement path file for the nozzle through slicing ideal rheological response of a printable ink during DIW. Areas
software, and 3) deposition of ink.[2,39] The key characteristic of different shear stress levels experienced by the ink during
valued in DIW is the ability to more freely customize the inks extrusion through the micronozzle are mapped with different
to print 3D structures at meso- and microscales with good pre- colors. Inside the nozzle, the shear stress is above yield stress,
cision. Machine parameters including nozzle size and printing hence the material yields and flows (Region 1). Outside the
speed influence printing accuracy and resolution (100–1200 µm nozzle, the stress has been removed, and the material trans-
for the x–y layer and 100–400 µm for z resolution; minimum forms to a viscoelastic solid (Region 2). Once the deposition
feature size ≈ 500 µm).[20] Typically, nozzles having smaller process ends, the printed structure must retain its shape until
diameters can enhance printing resolution; however, greater fully solidified. The ink should have appropriate rheology after
extrusion pressure and build time would be required to avoid printing to avoid the stacked filaments from sagging under their
nozzle clogging. Similarly, lower printing speed typically results own weight and reduce the bending of spanning parts. To limit
in better shape tolerances and fidelity, although it elevates the these phenomena, the value of storage modulus (G′) needs to
printing time. The uniqueness of the printing process is in be higher than the loss modulus (G′′) of the suspended ink.
its ability to extrude continuous filaments at room tempera- Moreover, for DIW inks, the value of G′ must remain nearly
ture since the printability does not rely on temperature rather constant over low shear stress, as shown in Figure 1b. This
depends on the rheological properties of the ink. As a result, is called the linear viscoelastic region (LVR). Two yield stress
optimizing the rheological make-up for the ink (discussed parameters (σ1 and σ2) can be optimized to gain further insight
further in Section 3) becomes critically important for DIW, into the behavior of the inks during the writing process: 1) σ1,
which can be achieved through various means, such as chem- indicating the onset of fall in the value of G′ (deviation of G′
ical modification of the ink, addition of rheological modifiers, from LVR), and 2) σ2, indicating the transition from solid-like
fillers, etc.[35,40] Once the ink exits the nozzle and before final to liquid-like behavior (crossover of G′ and G′′).[6]
deposition, it is not completely at rest; instead, the ink filament Several mathematical models have been developed to quan-
experiences bending and stretching to some extent. The degree tify the printability and shape fidelity parameters. The power-
of ink stretching can be controlled by tuning the ratio between law viscosity model is generally used to represent the non-
the extrusion rate (material extrusion) and printing speed linear relationship between shear stress and viscosity and is
(printhead movement ≈ 5–50 mm s−1).[39] After ink deposition, described by,
solidification occurs either naturally or assisted by an external
process, such as solvent evaporation, gelation, solvent-driven η = Kγ n −1 (1)
reactions, heat treatment, and photocuring.[2] Finally, DIW tech-
nology has the added benefit of minimal post-processing and where η is the viscosity, K is the flow consistency index, γ is
reduction in material waste, thus making the overall manufac- the shear rate, and n is the power law index. For shear-thinning
turing process more economical and sustainable. fluids, n fits the following parameter, 0 < n < 1, while for shear-
thickening, n > 1.
However, when yield stress is also considered, the power law
3. Ink Rheology is adapted with an additional term and mathematically repre-
sented by the Herschel-Bulkley (HB) model. Hence the flow
The fundamental capacity for DIW to form self-supporting behavior of ink for DIW is usually described using this model
extruded layers is a direct consequence of the ink’s printability given by,
and shape fidelity.[41] In general, an ink is printable if it can be
extruded as a continuous filament via a specific nozzle and τ = τ y + Kγ n (2)
can be used to create structures that exactly mimic the digital
model. The ink’s shape fidelity dictates how the morphology where τ is the shear stress and as described previously, K is the
of the printed structure should be preserved after deposition, flow consistency index, γ is the shear rate, and n is the flow
drying, and post-processing.[42] Furthermore, the ink must index.[35] It is required that the shear stress applied by the
flow smoothly without discontinuity or particle jamming that nozzle must exceed the yield shear stress so that the ink acts as
can otherwise clog the deposition nozzle. From a rheological a fluid and flows easily. Furthermore, when the shear stresses
standpoint, shear-thinning behavior at variable flow rates is in the form of (τ − τy) are plotted with respect to the estimated
required to fulfill these characteristics. Shear-thinning is the shear rates on a log–log graph, the values of n and K from the
non-Newtonian behavior of fluids whose viscosity decreases HB model can be determined. These values distinguish and
with increasing shear rate. Thus, it can help ink flow through optimize ink compositions based on their shear-thinning capa-
the nozzles even at lower extrusion pressures, assuring extrud- bility and viscosity and thus help to determine the ideal ink for
ability. Typically, the viscosity of the DIW ink falls between the DIW.[43]
Ideally, the ink’s characteristics should be solely determined and three-interval thixotropy tests are also performed to assess
by the shear rate, such that its structural integrity can be quickly the printability of inks.[44] The yield stress is often determined
restored when it stops flowing. However, for thixotropic mate- from oscillatory tests, as the value of stress at which the storage
rials, ink characteristics are affected by shear history and shear modulus equals the loss modulus (crossover point). These
rate.[44] For these materials, the HB model can be modified to physical parameters found empirically can be tuned accord-
the following: ingly by invoking material chemistry (e.g., advanced polymer
design) or adding plasticizers and/or rheology modifiers (e.g.,
n
τ = K γ t − m + τ 0 (3) silica) for ink formulation. Owing to the exclusive dependence
of DIW printability and shape fidelity on these parameters, they
where t is shearing time and m is a dimensionless thixotropic are of paramount importance for the successful completion of
index. However, the accuracy of this equation is limited when any DIW process.
estimating large values of time and when considering the
recovery of the ink’s viscosity once shear stress is removed.[45]
The maximum shear stress rate and the shear stress can also 4. Recent Advances in DIW of Advanced Materials
be estimated. For example, the maximum shear stress rate can
be approximated by, DIW of a wide variety of materials with drastically different
properties can lead to complicated process mechanisms. How-
4Q ever, through careful control of ink composition, rheological
γ max = (4)
πr 3 behavior, printing parameters, the final 3D geometry, and the
printing setup, structures can be constructed from a variety of
where r is the nozzle radius and Q is the volumic flow rate, cal- materials with significant and sophisticated features. The rapid
culated as Q = Sr 2, with S as the printing speed.[35] And estima- and ongoing engineering of novel materials, such as polymers,
tion of the shear stress (τ), assuming radial nozzle, is obtained ceramics, metals, cement, alloys, and composites, has propelled
through the following calculation: DIW to become one of the frontiers of current manufacturing
processes in the near future.
∆P
τ= r (5)
2L
4.1. DIW of Polymer-Based Structures
where ΔP is the pressure applied at the nozzle, r is the radial
position from the center to the edge of the nozzle, and L is the There exists a massive library of polymeric materials that can
nozzle length.[40] be printed via DIW. DIW of both synthetic and biopolymers as
A mathematical relationship had also been proposed to cal- well as composites have shown great promise for their possible
culate the minimum yield stress required to avoid sagging due applications in myriad engineering fields. The DIW technique
to self-weight and capillary forces. M’Barki et al.[41] expressed it is somewhat different from other polymer AM technologies
as: such as FFF, selective laser sintering (SLS), and stereolithog-
raphy in that the precursor polymeric ink, be it thermoplastic,
σ ydyn ≥ γ R −1 + ρ gh (6) thermoset, elastomer, or composites, can be extruded through
fine nozzles at room temperature without requiring melting,
where σ ydyn is the dynamic yield stress, γ is the suspension sur- selective sintering or additional binding prior to, or during
face tension, R is the nozzle diameter, and ρgh denotes the self- deposition. Therefore, while the other techniques are limited by
weight of the material. the type of polymers being printed, DIW is not.
Smay et al.[9] applied elastic beam theory on spanning ink
filaments to calculate the minimum storage modulus required
to mitigate deflection: 4.1.1. Polymer Resins
4
L DIW has been utilized to print thermoset polymers into any
G ′ ≥ 1.4γ   D (7)
 D shapes and forms with desired properties and functionalities.
Typically, during the printing of thermosets, curing occurs well
Here, γ is the ink’s specific weight, L is the length of the after deposition so that chemical or physical crosslinks form
spanning element, and D is its diameter. The ink’s Poisson between printed layers, potentially leading to drastic improve-
ratio was assumed to be 0.5 (incompressible). ments in bond strength between layers compared to printed
However, it is essential to note that these mathematically thermoplastics. Researchers, over the years, have managed to
derived models are not absolute and present the challenges overcome the difficulties in tailoring the viscoelastic properties
of finding a universal DIW rheological model. As such, the of thermosets to realize 3D structures with excellent structural
rheological properties of the ink are often assessed experimen- and functional behavior. An example of such a mechani-
tally via shear rheology using a rotational rheometer. Standard cally robust thermoset polymer is cyanate ester (CE) resins.
rheological tests such as flow ramps allow the evaluation of the Chandrasekaran et al.[18] facilitated the direct-write printing
degree of shear-thinning of inks, while oscillatory tests give of CE resins with well-architected structures at a large scale
information on the viscoelastic properties. Extensional rheology (Figure 2a-ii). They tailored the rheology of the CE ink through
Figure 2. DIW of polymer resins. a-i) 3D printing of gel DCPD solution that is solidified by frontal polymerization immediately after extrusion from
the print head (left). Free-form 3D-printed structures produced via frontal polymerization (right). Reproduced with permission.[19] Copyright 2018,
Springer Nature. ii) Mechanism of cyanate ester polymerization and the formation of triazine ring (top). 3D printed fully cured structures (bottom).
Reproduced with permission.[18] Copyright 2012, Royal Society of Chemistry. b) Schematic representation of the solvent-cast direct writing (SC-DW)
process with a thermoplastic solution showing deposition of the polymer solution through a micronozzle followed by rapid solvent evaporation (left).
Microstructures (middle) manufactured by SC-DW: top and side view virtual images of the programmed SC-DW fabrication of the square spiral, top
and side view SEM images of an actual PLA square spiral, inclined top-view SEM image of a PLA circular spiral, representative optical image of a PLA
scaffold composed of nine layers, inclined top-view SEM image of PLA 9-layer scaffold, and SEM image of a PLA cup. Tensile properties comparison
(right) for a straight fiber (dash line) and a microstructured fiber (solid line). Reproduced with permission.[52] Copyright 2013, Wiley-VCH. (c-i) Fabrica-
tion of PDMS-based architecture (left). Printed unit cells (right) for a programmable range of Poisson’s ratio values (upper row) and 3 × 3 unit cells
the addition of silica nanoparticles. A fivefold increase in elastic prepared colloidal photonic inks by dispersing silica particles
modulus was observed for the carbonized printed CE parts in UA, optimally formulated to simultaneously achieve the
compared to printed CE. Another traditional high-performance macroscopic rheological properties for printability and micro-
thermosetting polymer is bismaleimide (BMI), which could not scopic colloidal arrangement for structural coloration. This ink
be fabricated into 3D architectures due to its poor solubility. enabled them to print any macroscopic pattern of lines and
Therefore, expensive and precise molds were required to create faces. The microscopic colloidal arrangement is configured
even simpler structures from BMI. Wu[46] developed novel to be either amorphous or crystalline depending on the resin
hybrid inks to develop BMI architectures that were shown to viscosity to govern the colors’ iridescence. On the other hand,
possess high thermal stability and mechanical property com- Robertson et al.[19] found the traditional curing approach for
pared to commercial ones. This opens up the potential of thermosets to be slow and high-energy consuming. Therefore,
printing BMI architectures with desirable complexity in the aer- they introduced a promising alternative called Frontal poly
ospace and automobile industries. Usually, prepolymer resins merization, where a self-propagating exothermic reaction wave
containing thermosetting monomers, especially epoxy-based transforms liquid monomers to fully cured polymers. Using
thermosets, do not possess the required rheological characteris- frontal polymerization, they printed polydicyclopentadiene
tics for DIW. However, Manning et al.[47] added self-assembling (PDCPD), a crosslinked thermoset polymer with high impact
ureidopyrimidinone-modified Jeffamine D230 and nanoclay resistance, fracture toughness, stiffness, and chemical resist-
filler to attain suitable viscoelastic properties, facilitating direct- ance. This new technique should allow faster fabrication of
write assembly of the epoxy–amine thermosets. They proposed micro-architected parts and complicated 3D printed structures
that self-assembly may facilitate tunable viscoelastic behavior in beyond thermoset polymers (Figure 2a-i).
currently unprintable resins. Typically, thermoplastic feedstocks are liquefied in a heated
Beyond the developments of inks, researchers have imple- deposition nozzle prior to deposition, as is the case with FFF,
mented modifications of the printing process and post- or are selectively sintered in a powder bed using a laser (SLS).
processing in recent years. For instance, Guo et al.[48] noticed However, these processes are plagued with issues such as geo-
that previously printed polyimides showed high volume metric warping and residual stresses that arise in the 3D printed
shrinkage (more than 45%), which may hamper the imple- thermoplastic materials due to the strong thermal gradients
mentation of direct-writing of 3D parts with high dimensional during the printing process. One such thermoplastic polymer
accuracy. Therefore, to diminish the dimensional shrinkage, that has a growing demand for fabrication with intricate archi-
they fabricated polyimides using a two-stage curing strategy: tectures, particularly for bio-applications, is polylactide. Poly-
UV-DIW of polyimide ink, followed by thermal imidization lactides such as poly(lactic acid) (PLA), poly(lactic-co-glycolic
of the polyimide parts. More specifically, UV-curable precur- acid) (PLGA), and poly(glycolic acid) (PGA) are biodegradable
sors hydroxyethyl methacrylate (HEMA) grafted poly (amide thermoplastic polymers that are essential materials for medical
acid) (PAA) (PAA-xHEMA, in which x is the molar percentage devices such as cellular materials to support cell and tissue
of HEMA to carboxyl groups of PAA) were printed and ther- growth, pins to mend broken bones and more. Guo et al.[52]
mally imidized to form 3D structures. The printed structure developed the solvent-cast direct-write (SC-DW) fabrication
demonstrated a dimensional shrinkage below 6%. However, method, which allowed 3D geometries to be created at room
Zhu et al.[49] pointed out that UV-DIW faced a trade-off between temperature using dissolvable thermoplastic polymer, PLA, in
required curing intensity and effective range. They addressed a freeform fashion (Figure 2b). They used dichloromethane
this challenge by bringing in a near-infrared (NIR) laser- (DCM, boiling point = 39.6 °C) as the solvent due to its fast
assisted module that boosts the scalability of DIW to solidify evaporation characteristics and good PLA solubility. Solvent
deposited filaments with diameters up to 4 mm, far beyond evaporation plays a vital role in the geometric retention of the
that achievable by UV-DIW. Also, this approach introduced printed structure. As the solvent rapidly evaporates, the mate-
parallel manufacturing of multicolor and multiscalable fila- rial gains significant rigidity and allows freeform printing in
ments and free-standing objects. In this way, they printed epoxy the open air. Thus, they had presented a flexible, cheap, and
acrylate thermoset resins into a woodpile structure. In future powerful fabrication route to direct-write thermoplastic-based
work,[50] the relationship between scale and printing speed in microsystems with electrical, mechanical (Figure 2b), and/or
NIR-DIW was further established to print complex macroscale microfluidic functionalities. In a follow-up work, Guo et al.[53]
black objects within dozens of minutes. Another acrylate-based reported a comprehensive analysis of the rheological charac-
thermoset resin, urethane acrylate (UA), has been utilized to teristics of their thermoplastic solution ink, solvent evapora-
print customized structural-color graphics using DIW.[51] They tion kinetics, and effect of process-related parameters on the
of the corresponding PDMS-based architectures (lower row). Reproduced with permission.[57] Copyright 2015, Wiley-VCH. ii) Cross-sectional image of
a 3D printed simple cubic (SC) (top left) and face-centered tetragonal (FCT) structure under 25% compression. Cross-sections from 3D finite element
(FE) simulation showing stress distribution in SC structure (bottom left) and FCT structure (bottom right) under simulated compressive condition.
Color-scale (bottom) shows compressive stress (negative) and tensile stress (positive). A continuous load column forms in the SC structure, whereas
the load path in the FCT structure is staggered. Reproduced with permission.[34] Copyright 2014, Wiley-VCH. d) Schematic illustration of DIW of silk
fibroin in a liquid reservoir (left), DIW of silk fibroin in the form of square lattice (middle) and 3D circular web (right). Morphological modulation of
human bone marrow derived stem cells seeded on direct-write scaffold with chondrogenic differentiation. Images show gradual overall change of cell
morphology from spread to aggregated from Day 1 to Day 21. Immunofluorescent staining (red in color) shows cytoskeletal protein actin. Reproduced
with permission.[31] Copyright 2008, Wiley-VCH.
crystallization of the extruded filaments. The thermoplastic and prone to failure. On the other hand, stress diverges at each
solution ink showed a shear-thinning behavior inside the of the intersections in the FCT structure due to the staggered
nozzle, and the process viscosity was dependent on the polymer structural arrangement where the load path is more broadly
content. Also, they found that the internal diffusion of the sol- distributed than the SC columns, resulting in a lower stress
vent through the filaments controlled the solvent removal of response (Figure 2c-ii). In this way, microarchitected structures
the extrudates. Faster solvent evaporation could be achieved with well-controlled directional properties are achieved, which
by decreasing the diameter of extrudates, which could be real- could be utilized in mechanical energy absorption applica-
ized by increasing the print velocity or decreasing the applied tions. Using silicone-based elastomeric ink, Clausen et al.[57]
pressure and nozzle diameter. On the other hand, slow solvent printed topology optimized auxetic materials. Although aux-
evaporation during the filament drying stage helps the PLA etic materials exhibit unusual mechanical behavior, the desired
to complete the crystallization process, ultimately resulting in response is only observed over a narrow range of strains (less
the rapid formation of 3D freeform microstructures, including than a few percent) and are difficult to manufacture in a scal-
a nine-layer scaffold, layer-by-layer tower, and freeform spiral. able manner. The work of Clausen et al. can be readily taken
Thus, this method offers a new perspective for manufacturing as a solution to these challenges. Using DIW, they were able
complex microstructures from thermoplastic polymer solutions to fabricate those structures, shown in Figure 2c-i, with pro-
and provides guidelines to optimize the various parameters for grammable Poisson’s ratios ranging from −0.8 to 0.8 over large
3D geometry fabrication. Besides, polylactides have also been deformations of 20% or more. Qin et al.[60] investigated the
3D printed using surface-tension-driven DIW to build tissue mechanical behavior of 3D printed spider-web mimics to deter-
engineering scaffolds.[54] More recently, the thermoplastic PLA mine how web mechanics are controlled by their topological
has also been combined with poly(3,4-ethylenedioxythiophene) design and material distribution. DIW, in this case, paved the
(PEDOT) to compose graft copolymers as 3D printable mate- way to pattern a single elastomeric material into complex web
rials equipped with biocompatibility and electronic conduc- structures that would be cumbersome, if not impossible, with
tivity.[55] The SC-DW method can also be extended to print existing fabrication methods. Their study reveals that the web
other thermoplastic polymers and thus facilitates a wide range strength depends on the material distribution, offering insight
of applications, including stimuli-responsive materials, tissue into the observations of the thickness ratio of individual radial
engineering scaffolds, and microelectronic devices. Another and spiral threads within the natural spider webs. Thus, they
thermoplastic polymer often demanded in high-temperature identified pathways to print elastomeric materials structures
applications is the all-aromatic polyimides, owing to their high with maximum strength, low density, and adaptability. Further-
degradation temperatures, excellent mechanical strength, and more, DIW has also been modified to print architected elasto-
chemical resistance. However, their all-aromatic structure hin- meric foams. Visser et al.[61] created a modification called direct
ders DIW because of their insolubility in organic solvents. To bubble writing, where a core–shell nozzle was used to extrude
address this, Rau et al.[56] utilized UV-curable inks through a low viscosity polyethylene glycol diacrylate (PEG-DA) solution
cross-linking assisted DIW to print polyimides (also known as around a gas. To vary between open and closed-cell structures,
Kapton) with complex 3D structures such as trusses. For suc- oxygen-rich and oxygen-deficient gases (such as nitrogen) were
cessful printing, they had to induce an amide-to-imide trans- used, respectively. Modifications in the volumetric flow rate
formation by heating the amide polymer monolith to a high and gas pressure allowed further customization of the resultant
temperature after in situ crosslinking-assisted DIW. These foams, including tunable stiffness, ejected bubble dispersion,
printed structures possessed high thermal stability making and filament width. Optimization of these printing parameters
them ideal for aerospace and military applications. generated vertical pillars with up to 40° of inclination and was
Alongside thermoset and thermoplastic polymers, DIW has used to fabricate custom pressure sensors with increased elec-
been harnessed to create structures with elastomeric mate- trical conductivity, stiffness, and compressive strength. Another
rials. These materials have been utilized to demonstrate the aspect of the design freedom of DIW is that it can be used to
freedom of design of DIW with an emphasis on how micro extrude silicone-based ink onto nonuniform and uneven sur-
architectures and topology can tailor the mechanical and func- faces accurately. The DIW print setup can be customized such
tional behavior of the printed elastomers.[58,59] By employing that auxetic materials can be printed on irregular double-curved
DIW, one can carefully control the elastomeric structure to and inflatable surfaces. It can also be modified to print elas-
create mechanical metamaterials or other sophisticated archi- tomeric materials into a support media, particularly for those
tectures. Duoss et al.[34] demonstrated the ability to indepen- elastomers, which have long gelation/curing time and can flow
dently tailor mechanical (compression and shear) response in upon printing, such as polydimethylsiloxane (PDMS). Although
3D printed elastomers via micro-architected design. They have Qin et al.[60] used PDMS to print the spider webs, the low elastic
printed two cellular architectures—simple cubic (SC)-like struc- modulus of the pre- and postcured PDMS, and its deformation
ture and face-centered tetragonal (FCT) configuration. Note that under gravity restricts the print of 3D complex geometries with
it is challenging to produce cellular solids with well-controlled self-supporting monolithic structures. To address this chal-
directional properties. However, the structures developed in lenge, Hinton et al.[62] printed hydrophobic PDMS resins within
this work exhibit markedly distinct load responses with direc- a hydrophilic carbopol gel support. The support media yields
tionally dependent behavior, including negative stiffness. For and fluidizes when the syringe tip of the 3D printer moves
instance, in the case of printed SC structures under compres- through it but acts as a solid for the PDMS extruded within it.
sion, columnar stress concentration paths developed at each In combination with the immiscibility of hydrophobic PDMS in
interlayer filament intersection, which is inherently unstable the hydrophilic support, this mechanism confines the complex
shaped PDMS elastomer while maintaining dimensional sta- dissolved BC in an ionic liquid (1-ethyl-3-methylimidazolium
bility. After printing and curing, the support media can be acetate) to direct-write complex patterns of 2D structures, fol-
removed using suitable solutions. The results demonstrate that lowed by coagulation of a nonsolvent. Their method enabled
hydrophobic polymers with low viscosity and long cure times the fabrication of spatially tailored gel structures made of bac-
can be 3D printed37 using hydrophilic support, thus expanding terial cellulose with a wide range of biomedical applications.
the range of materials library that can be used for DIW. Agarose (purified Agar), a galactose-based polysaccharide, is
Besides synthetic polymers, there is growing interest in the also a natural biopolymer derived from seaweed and red algae
use of biopolymers with user-defined mechanical and biochem- such as Gelidium and Gracilaria. DIW of agarose has enabled
ical properties for the production of ecofriendly sustainable the building of one of the first fully biological vascular tubular
products.[63] At the same time, the use of synthetic polymers in grafts by Norotte et al.[67] They were able to engineer a reliable,
biomedical industries has several possible negative factors such accurate, and scalable scaffold-free tissue fabrication technique
as harmful breakdown products, released additives, decreased to print compositionally intricate structures with complex
cell attachment, degradability, and recyclability. As a result, the branching geometry and multiple layers of tubes.
utilization of natural biopolymers, such as lignin, starch, cellu-
lose, hemicellulose, chitosan, alginate, and their derivatives as
3D printing feedstocks not only enables sustainability but also 4.1.2. Polymer Composites
reduces the possible negative impacts of the use of synthetic
polymers in biomedical applications. A natural biopolymer Due to the intrinsically limited mechanical properties and func-
with excellent biocompatibility, superior mechanical toughness, tionalities of printed pure polymer parts, there is a critical need
and high modulus is the silk fibroin protein. Ghosh et al.[31] to develop printable high-performance polymer composites.
presented the direct-write printing of this protein-based mate- DIW has enabled significant advances in the development of
rial by developing an ink from aqueous solutions of regener- these composites due to its precise control of the position, ori-
ated Bombyx mori silk. The scaffolds supported human bone entation, and concentration of the reinforcements. These rein-
marrow-derived mesenchymal stem cell (hMSC) adhesion and forcements can be in various geometries, such as spherical or
growth (Figure 2d). This enabled the fabrication of 3D micro irregular particles, fibers, and platelets.[68–70]
periodic scaffolds and opened the pathway towards printing Due to easy processability and low cost, particle reinforce-
protein-based microarchitecture designs for tissue engineering ments have been widely explored for DIW of polymer com-
using DIW. Beyond protein-based materials printing, DIW has posites. Particles with length scales ranging from nanoscale to
also been explored for cellulose-based materials. Cellulose is several microns have been incorporated in the DIW ink. These
one of the most abundant polymers on Earth and is found in filler materials often serve as rheological modifiers as well as
many biological organisms. Most previous efforts to print this mechanical reinforcements. Furthermore, DIW, thanks to its
material were primarily focused on hydrogel-based inks con- versatility, allows the mixing of particles with selective func-
taining nanofibrillated cellulose with low concentrations. How- tionalities for intended applications. For example, carbon-based
ever, Siqueira et al.[40] formulated viscoelastic concentrated inks nanomaterials such as graphene and CNTs can be seamlessly
of anisotropic cellulose nanocrystals (CNC) that facilitated the added to the polymeric ink for printing multifunctional 3D
direct-write fabrication of textured cellular architectures with composites. Typically, the high electrical conductivity of these
enhanced mechanical properties. In the printed structures, they materials is exploited to render conductivity in the insulating
observed micro-reinforcement effects, similar to that in plant polymer matrix;[71,72] however, other functionalities can also be
cell walls, due to the shear-induced alignment of the CNC par- achieved. Jakus et al.,[29] for example, developed a graphene
ticles during DIW, resulting in enhanced stiffness. Similarly, reinforced polylactide-co-glycolide composite. This composite,
DIW was also used to print pure cellulose nanocrystal (CNC) while displaying high electrical conductivity, was mechanically
aerogels with minimal shrinkage or damage during produc- flexible, biocompatible, neurogenically bioactive, and biodegrad-
tion. Li et al.[64] showed that increasing CNC concentration able (Figure 3c). Researchers have also explored various carbon
improved the quality and resolution of the final structure. nanotube (CNT)–polymer composites, in which CNTs have
The incorporation of hierarchical porosity was also designed been incorporated in both thermoplastic[73] and thermoset[74]
to facilitate cell integration for tissue scaffolding applications. elastomers. In most cases, the printed composites have been
These observations take us another step forward towards sus- used for various sensing applications such as strain sensor,[75]
tainable materials for 3D printing. Another technique to print liquid sensor,[76] and piezoresistive sensors.[73] Chen et al.[77] uti-
cellulose in high concentration was proposed by Pattinson and lized DIW to print PDMS/CNTs composites with customizable
Hart.[65] They used cellulose acetate (CA) as the feedstock and material properties through the creation of trimodal and hierar-
then converted the finished part to cellulose by deacetylation chical porosity. The printed nanocomposites demonstrated that
using sodium hydroxide (NaOH) treatment. Their technique a single object could be fabricated with different regions having
rendered parts with high toughness and isotropic strength. The different electrical conductivity. This capability of DIW opens
process also enabled DIW of antimicrobial agents that kill or the pathway towards controlling local property or functionality
inhibit the growth of microorganisms while causing little or no in the structure, such as conductivity gradient, strength gra-
damage to the host. Due to their remarkable features such as dient, elasticity gradient, etc. Customizing the printing pro-
ability to survive in hostile environments and adaptive mechan- cess can offer additional benefits for CNTs–polymer composite
ical properties, bacterial cellulose (BC) has garnered significant processing. For instance, CNTs–polyurethane (a UV curable
attention from the scientific community. Markstedt et al.[66] polymer) composites having high specific rigidity and electrical
Figure 3. DIW of polymer composites. a) Schematic of controlled ferromagnetic particle reinforcement in 3D printed soft materials. The ferromagnetic
particles embedded in the composite ink are reoriented by the applied magnetic field generated by a permanent magnet or an electromagnet placed
around the dispensing nozzle. A reconfigurable soft electronic device on the annular ring structure exhibiting different electronic functions depending
on the direction of an applied magnetic field of 30 mT. A hexapedal structure stopping and holding a fast-moving object (glass ball of diameter 18 mm
and weight 8 g) upon application of a magnetic field generated by a permanent magnet. A hexapedal structure wrapping an oblong pharmaceutical pill
and carrying the pill using rolling-based locomotion under a rotating magnetic field generated by a permanent magnet. Horizontal leap of a 3D auxetic
structure upon sudden reversal of the applied magnetic field direction while attenuating the field strength by rotating a permanent magnet by 90°.
Reproduced with permission.[84] Copyright 2018, Springer Nature. b) Schematic of rotational DIW process for fabricating damage–tolerant fiber–rein-
forced polymer composite. The technique offers an added control on fiber orientation inside the polymer matrix during printing through the rotating
nozzle to achieve a helical pattern, where the helical angle is dictated by the rotational rate (ω) and translational velocity (v). X-ray microtomography
images show that when no rotation is applied, the fiber orientation is highly uniform and nearly parallel along the print path. In contrast, structures
printed at high rotation rates exhibit a more random fiber orientation and nearly isotropic elastic properties. The anisotropic fiber arrangement leads
conductivity can be manufactured by UV-assisted DIW.[74] dymium–iron–boron (NdFeB) alloy microparticles within the
These works demonstrate the flexibility and customizability of silicone resin structure. Figure 3a demonstrates the process
the printing process. of controlling the ferromagnetic particle arrangement inside
Beyond graphene, other 2D materials can also be incorpo- the soft polymer matrix. This novel DIW technique introduced
rated in the polymer matrix via DIW, which results in enhanced programmable ferromagnetic domains in the soft materials
properties and/or functionalities. For example, hexagonal that enable fast transformations between complex 3D shapes,
boron nitride (hBN)–polymer composite has been developed by previously inaccessible via standard manufacturing. These
DIW.[78] These composites had high thermal conductivity due to include a) substrate-free, remote magnetic actuation, b) fast
the alignment of hBN along the printing direction owing to the and fully reversible transformation from 2D planar structures
shear-inducing effect of DIW. Cheng et al.[79] printed polyeth- to 3D shapes, and c) the capability to selectively choose the
ylene oxide (PEO) composites containing aligned silane-treated parts within the structure should actuate. The researchers
hexagonal boron nitride (S-hBN) platelets without the need for found that compared to the currently available 3D-printed
organic solvents. Remarkably, the polymer composites were shape-transforming soft materials, the performance of the DIW
observed to have a greater thermal conductivity (1.031 W−1 K−1), printed magnetic structures were orders of magnitude supe-
nearly double that with random platelet arrangement. Nanoscale rior: deforming up to strains of 0.15–0.25 within 0.1–0.5 s while
layered silicates (nanoclay)[80] are promising filler materials for providing a power density of 22.3–309.3 kW m−3.
polymer matrix composites.[81] Hmeidat et al.[82] was the first The other commonly used reinforcements for polymer com-
to investigate nanoclay–polymer (epoxy) nanocomposites. The posites are various synthetic and natural fibers[86,87] that are
strength of these 3D-printed epoxy nanocomposites ranged utilized to fabricate lightweight, high-performance compos-
from 80 to 143 MPa, substantially higher than that of other ites.[70] Compton et al. developed an epoxy polymer composite
reported values for 3D-printed thermoset composites. Johnson via DIW by incorporating silicon carbide whiskers and carbon
et al.[83] captured multiscale and temporal morphology and fibers (CF). Inspired by nature’s balsa wood architecture, the
dynamics within thermoset composite ink (layered silicate– composite structure involves an interconnected network of
epoxy composites) to determine the effect of the printing pro- solid struts forming edges or faces of cells. Like the natural
cess on the morphology and recovery dynamics of the printed structure, the composite exhibited exceptional mechanical
material in real time. The dynamics of the silicate particles strength—nearly four times greater—compared to its pure
during recovery were observed to be anisotropic, reflecting polymer counterpart. DIW proved essential as it allowed for
nanoscale structural alignment induced during the extrusion controlled alignment of the reinforcements as well as complex
and deposition processes. Another material, magnetite, is used geometry unattainable via conventional manufacturing. Lewicki
as a conductive reinforcement to strengthen polymer as well as et al.[70] found the exciting possibility of aligning carbon fiber
provide irradiation and electromagnetic shielding, thus, proving in a high-performance thermoset by taking advantage of the
useful for electronic applications. Restrepo and Colorado[68] shear force induced by the nozzle during the extrusion pro-
printed commercial diglicydyl ether of bisphenol A (DGEBA) cess of DIW. Control over the alignment demonstrated more
epoxy polymer resin incorporating these magnetite particles. mechanically robust polymer composites that outperformed the
Using DIW, the researchers were able to not only create geo- randomly oriented carbon-fiber composites. The increase in the
metrical configurations but also better distribute the particles tensile modulus of the composites, compared to their randomly
without the use of any other additive. In their study, the ideal oriented counterpart, was found to be 37%, despite having
percentages of this particulate material in the composite were equal reinforcement vol%. The alignment of CF was found to
found to be between 60% and 68% for successful printing. be beneficial not only for customizable strength and stiffness
The composites exhibited competitive mechanical properties but also to predict and delay fiber pullout and overall failure of
(compressive strength and ductility) even though the process the printed structure. Pierson et al.[88] showed that the DIW pro-
was not vacuum assisted, enabling them to be used on a large cess for epoxy/chopped carbon fiber composites can simultane-
scale and in structural applications. In addition to improved ously achieve a high degree of fiber alignment and a low degree
reinforcement distribution, DIW can give researchers higher of porosity. Thus, they reached 90% of the theoretical tensile
design freedom in customizing the arrangement of reinforce- modulus and 66% of the theoretical tensile strength for a fully
ment particles within the polymer matrix. In particular, Kim aligned composite. However, the maximum short fiber loading
et al.[84] modified the standard DIW technique by applying a in this work was limited to less than 5% by volume. Exceeding
magnetic field during printing to orient the conductive neo- fiber volume fraction over 5% resulted in nozzle clogging and,
to anisotropic elastic properties. Top surface and cross-sectional views of punctured composites printed without and with rotation, in which the helical
arrangement of fibers (akin to those found in osteons in bone) present in the latter sample resulted in a much smaller damaged region and less damage
penetration, respectively than the samples printed without rotation. Reproduced with permission.[85] Copyright 2018, National Academy of Sciences.
c) Graphene–polylactide-co-glycolide composite inks are produced through simple combination and mixing of the elastomer solution with the disper-
sion of graphene powder in a graded solvent followed by volume reduction and thickening. The ink can be extruded to create user-defined architectures
(high fidelity 3D scaffolds, self-supporting tubular structures, flexible, complex, and conductive architectures) having a variety of potential applications,
including those relating to energy storage and bioelectronics, as well as tissue and organ engineering. Photograph (right) of tubular nerve conduit that
was implanted into a human cadaver via longitudinal transection and wrapping around the ulnar nerve (white arrows). The printed nerve conduit was
then sutured closed along the longitudinal transection (white dotted line) as well as to the surrounding epineurium and nerve tissue (inset, yellow
circle). Reproduced with permission.[29] Copyright 2015, American Chemical Society.
thus, failure of fabrication. Nozzle clogging is a challenge fre- fabrication methods, such as particulate leaching and solvent
quently faced by DIW practitioners while printing fiber-rein- casting, cannot generate complex features in the biopolymeric
forced polymer composites.[89] This challenge can be overcome 3D constructs such as adequate pore size, biodegradability,
by engineering the materials being printed or customizing the interconnectivity, bioactivity, and mechanical properties as
print setup. Jiang et al.,[90] for example, engineered the mate- required for biomedical and tissue engineering applications.
rials while printing natural flax fiber–reinforced polymer com- These methods were also limited due to the use of highly toxic
posite. Using the sonication process, they removed the outer solvents. However, in recent years, DIW has enabled the fabrica-
layer of the fiber and dispersed the processed fiber uniformly tion of 3D scaffolds with appropriate characteristics for specific
in the elastomer to form a homogeneous ink, which overcame applications. For example, in bone tissue regeneration, it pro-
the nozzle clogging issue. With the addition of only 0.2 wt% vides better control over porosity and pore size and offers large-
surface-modified flax fibers, the tensile properties could be scale reproducibility of scaffolds. Also, DIW has been combined
increased over 100%, which is comparable to other synthetic with imaging techniques, such as magnetic resonance imaging
fiber-reinforced composites with much higher fiber loading (MRI), to allow the fabrication of specific bone tissues with
fractions. On the other hand, Nawafleh and Celik[91] customized accurate 3D architectures. Polylactic acid (PLA) is a Food and
the print setup. They developed a vibration integrated auger Drug Administration (FDA)-approved biodegradable polymer
extrusion system that allowed the printing of highly viscous with a wide variety of biomedical applications. However, most
composite inks with fiber volume content from 5% to 46%. of the previously 3D printed PLA-based scaffolds required either
Using the customized DIW system, they could print without molecular modifications, melting, or subsequent processing
flow inconsistencies and nozzle clogging issues and achieved to remove the solvent. Overcoming these challenges, Serra[92]
exceptional isotropic mechanical performance in the printed reported DIW of highly porous PLA/bioglass 3D biodegrad-
composites. They hypothesized that a transformation takes able scaffolds. They combined G5 glass particles and polyeth-
place at high fiber volumes on the load transfer mechanism ylene glycol (PEG) with the PLA matrix to obtain composite
within the composites, leading to higher levels of strength and structures with excellent mechanical and bioactive properties.
stiffness enhancement. This pseudo transformation can give On the other hand, PLA’s applications have also been limited
rise to short fibers acting as if they are longer, which aids in by its weak mechanical properties. Zhang et al.[93] mixed PLA
the effective transfer of tensile loads from the matrix phase to with hydroxyapatite (HA), a reinforcing material that enhanced
the fibers. Easy customizability of the print setup offers other the mechanical properties of the resulting polymer composite.
benefits as well, such as spatial variation in composition and The macroporous PLA/HA scaffolds showed great potential for
the integration of microstructure and structural features. Col- promoting bone formation and may get utilized as graft substi-
lino et al.[15] used acoustically excited microfluidic print noz- tutes in reconstructive surgery. Another natural biopolymer is
zles to tailor the microstructure of printed composite filaments Alginate, usually extracted from brown seaweeds. Diogo et al.[94]
consisting of silicon carbide (SiC) fibers, solid barium titanate combined alginate with beta-tricalcium phosphate (β-TCP)
(BaTiO3) spheres, or hollow silicon oxide (SiO) spheres in an to produce composite scaffolds with superior biological and
epoxy matrix. The results demonstrate that acoustic focusing mechanical properties. Using DIW, they were able to model scaf-
is a favorable technique to control the fibers and microparti- folds that accurately match a specific bone defect. Alginate had
cles, and deposit two-phase ordered structures using a single also been used with single-walled carbon nanotubes (SWCNTs)
nozzle. Even modest volume fractions of acoustically focused for DIW of composite scaffolds with improved mechanical
and concentrated SiC fibers can produce printed composite fila- strength. CNTs have also been mixed with nanocrystalline
ments with excellent mechanical strength. External fields, e.g., hydroxyapatite (HA) in polycaprolactone (PCL) matrix to fab-
magnetic fields[13] have also been combined with DIW to create ricate biopolymer composites. The printing technique allowed
polymer architectures in which fiber orientation is controlled them to produce composites containing an interconnected net-
precisely. These approaches typically generate composites that work of near-square pores. Jakus et al.[29] utilized the biocom-
possess a nearly uniform fiber alignment within the matrix. patible elastomer, polylactide-co-glycolide, to develop a liquid
On the other hand, natural composites show that exceptional ink of graphene-based composite. They used the ink for DIW
mechanical performance can also arise from nonuniform/com- of graphene-based structures under ambient conditions. The
plex fiber arrangements. Inspired by these natural systems, resulting structures showed great potential for the fabrication
Raney et al.[85] developed a rotational DIW method that ena- of bioelectronics due to their superior electrical conductivity and
bles spatially controlled orientation of short fibers in polymer mechanical robustness. Another natural biopolymer, collagen,
matrices solely by varying the nozzle rotation speed relative to is also widely used in tissue regeneration procedures. It is the
the printing speed (Figure 3b). A rotating Luer lock coupling primary protein component sustaining the structure of the
was joined to the end of the syringe, which enables the nozzle extracellular matrix (ECM), but suffers from poor mechanical
to rotate freely relative to the syringe barrel. Using this method, properties. To overcome these deficiencies, Lee et al.[95] printed
they fabricated CF–epoxy composites with programmable- a mixture of two biopolymers, collagen, and alginate, which was
defined fiber arrangements, microstructural complexity, and coated with silica, thus forming a biomimetic composite. They
superior mechanical performance, e.g., enhanced damage toler- suggested that these collagen/alginate/silica biocomposites have
ance (Figure 3b). great potential to generate hard tissues. Magnetic iron oxide
Development of 3D composite structures using biopoly- (Fe3O4) nanoparticles also have crucial applications in the bio-
mers via AM and their promising application in different areas medical field due to their excellent biocompatibility and specific
are of huge academic and environmental interest. Traditional physical properties. Zhang et al.[96] mixed mesoporous bioactive
glass/polycaprolactone (MBG/PCL) with Fe3O4 nanoparticles to In the case of physically crosslinked hydrogels, the defining
prepare an injectable paste of Fe3O4/MBG/PCL. This prepared feature of physically crosslinked hydrogels is their revers-
paste enabled them to fabricate 3D biopolymer composites with ibility- the ability for the interactions to break and reform easily
high porosity and superior compressive strength. To increase upon exposure to stimuli like temperature or humidity. Thus,
biocompatibility and material sustainability, researchers have physical crosslinking can aid in printing hydrogels with prop-
also looked towards cellulose-based aerogel advancement for erties like swelling resistance and stretchability. For example,
biomedical and cosmetic applications.[97] Li et al.[98] created Chen et al.[33] used DIW to print a photonic hydrogel system
defibrillated and 2,2,6,6 tetramethyl-1-pipridinyloxy (TEMPO) that is physically cross-linked via a crystalline colloidal array.
modified cellulose nanofiber aerogel with a porosity of 98% and Specifically, hydrophilic linear poly(acrylamide) chains were
density of 26 mg cm−3 after freeze-drying. The final structure physically crosslinked using uniformly distributed colloidal
was 80% compressible in water prior to densification. Overall, spheres as reinforcements. This resulted in more uniform and
DIW of biopolymer composites opens up ample opportunities stable hydrogels with high stretchability (above 2800%). Chen
in a multitude of applications, ranging from biomedical engi- et al. were able to display this phenomenon through the pro-
neering to bioelectronics and more (Table 1). duction of freestanding structures that sustained the optical
properties and mechanical integrity of the underlying hydrogel.
This demonstrated that DIW hydrogels show promise for more
4.1.3. Hydrogels intricate applications like wearable and printable devices. Jiang
et al.[110] created hydrogel architectures from κ-CA and PVA
Hydrogels have been of great interest to 3D printing for appli- that were physically crosslinked via hydrogen bonding and van
cations such as drug delivery, tissue engineering, actuators, der Waals forces initiated during crystallization of PVA. This
and flexible electronics.[102] They are naturally or synthetically hybrid hydrogel ink had excellent rheological properties suit-
derived colloidal gels formed via cross-linking of polymer able for DIW that allowed for tailoring exceptional biocom-
chains and dispersed in a water-based medium. Typically, the patibility and bioactivity in the printed structures, in conjunc-
classification of hydrogels is based on the following charac- tion with high strength and resistance to swelling. Therefore,
teristics: physical structure (i.e., amorphous, crystalline, etc.), these printed hydrogels can be desirable for biomedical appli-
ionic charge, synthesis route (i.e., homopolymers, copoly- cations and devices like scaffolds that require a high level of
mers, multipolymers), size (i.e., macro-, micro-, nano-), and customization and accuracy. Liu et al.[109] developed printable
bonding.[103] As a result of their unique composition, hydrogels physically crosslinked hydrogel inks with programmed bacte-
offer material properties including biocompatibility, biodeg- rial cells as responsive components into multiscale living mate-
radability, hydrophilicity, and softness, particularly useful and rials, where the cells can communicate and process signals
favorable for biomedical and biomaterial applications. in a programmable manner. 3D printing programmed cells
Regarding their utilization for DIW, hydrogels present enable exploring novel living devices such as a living tattoo
exciting opportunities due to the ability to readily construct (Figure 4a). For instance, Barry III et al.[111] printed photopolym-
complex structures that can be fine-tuned for intended appli- erizable hydrogel scaffolds with the filament diameter, spacing,
cations. To successfully print hydrogel inks, optimization of number of layers, and geometry using a physically crosslinked
the crosslinking is crucial for extrusion, print resolution, and photocurable ink, which is well-suited for tissue engineering
accuracy since crosslinking significantly affects the mechan- applications (Figure 4b). In these ways, physical crosslinking
ical performance and stability of the final printed structure. aids the fabrication of unique hydrogel structures with excep-
Chemical crosslinking intermolecularly or intramolecularly tional properties and functionalities. The integration of DIW
links chain molecules together through covalent bonds, which and available functionalities from diversified hydrogel families
raise the molecular weight of the base polymer. Furthermore, it render an enriched fabrication platform for a myriad of sophis-
increases the number of entanglements between the polymer ticated applications.
chains, thereby influencing their flow behavior. Typically, cova- Compared to physically crosslinked hydrogels, chemically
lent crosslinking induced supramolecular assemblies result crosslinked hydrogels are typically stronger and more perma-
in the increase of the polymer viscosity, thereby influencing nent due to covalent bonds that dominate the interaction and
the overall ink rheology.[104,105] Generally, crosslinking can bonding between the hydrogel components/materials. Relatively
be classified into two main categories: physical and chemical poor mechanical properties of physically crosslinked hydrogels,
crosslinking. Physical crosslinks can be described primarily by together with their other limitations such as inadequate water
Van der Waals interactions, including ionic/electrostatic inter- sorption properties, make them incompatible for load-bearing
action and hydrogen bonding,[106] while chemical crosslinks tissue engineering applications. To address these limitations,
covalently bond the polymer branches by initiating reactions the incorporation of different types of nanocellulose, such as
such as photopolymerization, enzyme-induced crosslinking, bacterial nanocellulose (BC), cellulose nanofibers (CNFs), and
and “click” reactions like Michael type-addition.[106] In some cellulose nanocrystals (CNCs), into the chemically crosslinked
cases, crosslinking may be induced by external stimuli such regenerate silk fibroin (RSF) hydrogel matrix demonstrated
as temperature (i.e., agarose gel is thermally cross-linkable[107]) improved mechanical properties without compromising its
or UV-irradiation such as when a photoinitiated polymer is biological properties.[112] The hydrogels were fabricated using a
used.[108,109] For these scenarios, it is important to consider the 20 wt% silk fibroin composition with added nanocellulose dis-
effect of the stimuli on ink rheology as this directly impacts the persions, which were then chemically crosslinked via a photo-
ink’s printability. chemical method. It was found that the extrusion process of
Table 1. Summary of recent progress in DIW of polymers and polymer composites.
Classifier Material Key features Potential applications Refs.

Single polymers Synthetic polymers Thermosets Cyanate ester (CE) resins Fivefold increase in High-performance Chandrasekaran et al.[18]
modulus of elasticity, structural applications in
impressive thermo-oxidative extreme environments.
stability
Poly(4,4′-oxidiphenylene Printed truss structures, Multifunctional Rau et al.[56]
pyromellitimide) storage modulus above 1 components, such as 3D
(PMDA-ODA) GPa up to 400 °C integrated electronics
PI
Bismaleimide (BMI) High thermal stability and Automobile industry to Wu[46]
mechanical property com- aerospace
pared to commercial BMIs
Epoxy–amine Self-assembling ureidopy- Tunable viscoelastic Manning et al.[47]
rimidinone-modified Jef- behavior in currently
famine D230 and nanoclay unprintable resins
filler
Hydroxyethyl methacrylate Dimensional shrinkage less Aerospace, automobile, Guo et al.[48]
(HEMA) grafted polyamic than 6% microelectronics, and
acid (PAA) engineering
Polydicyclopentadiene High impact resistance, Faster and more efficient Robertson et al.[19]
(PDCPD) fracture toughness, manufacturing of high-
stiffness, and chemical performance polymers
resistance
Thermoplastics Poly(lactic acid) (PLA) Development of solvent- Microsystems with Guo et al.[52]
cast direct-write (SC-DW) electrical, mechanical,
method and/or microfluidic
functionalities
Poly(lactic acid) (PLA) Elucidating the phase New perspective for Guo et al.[53]
behavior and rheological manufacturing complex
properties of the inks structures from polymer
solutions
Poly(lactic acid) (PLA) Enabled production of Tissue engineering Berry et al.[54]
fibers with microvascular- scaffolds
scale diameters
Poly(3,4-ethylene Conductive and bio- Tissue engineering & Dominguez-Alfaro
dioxythiophene) (PEDOT) compatible printed patterns biomedical applications et al.[55]
Elastomers Silica-filled, Porous, microarchitected Mechanical energy Duoss et al.[34]
polydimethylsiloxane paste design, distinct load absorption
response, directionally
dependent behavior, nega-
tive stiffness
Poly(dimethylsiloxane) Programmable Poisson’s Targeted applications in Clausen et al.[57]
(PDMS) silicone ratios from −0.8 to 0.8 over aerospace, automotive,
20% strain and more biomedical, and acoustics
industries.
Poly(dimethylsiloxane) Complex web structures; Reinforcement of Qin et al.[60]
(PDMS) silicone web mechanics controlled composite materials,
by topological design and scaffolds for biomedical
material distribution applications or space
exploration
One-part acetoxy silicone Leakage-free connections, Automatable fabrication Su et al.[59]
T-shaped intersections, and of multimaterial mixers,
overlapping channels microfluidic-integrated
sensors, automation
components, and 3D
microfluidics
Table 1. Continued.

Sylgard 184 Linear and helical filaments, Microfluidics, cell Hinton et al.[62]
poly(dimethylsiloxane) 3D printed tubes were culture scaffolds, flexible
(PDMS) manifold and perfusable electronics, and medical
devices.
Biopolymers Regenerated Bombyx Printing protein-based Tissue engineering Ghosh et al.[31]
mori silk microarchitecture design constructs
Anisotropic cellulose Microreinforcement Sustainable materials with Siqueira et al.[40]
nanocrystals (CNC) effects like in plant cell cellular architectures
walls, tailored mechanical
properties
Cellulose acetate (CA) High toughness and Antimicrobial objects Pattinson and Hart[65]
isotropic strength
Bacterial cellulose (BC) Spatially tailored gel Packaging, medicine Markstedt et al.[66]
structures, complex tablets, scaffolds for tissue
patterns of 2D structures, engineering, and sensors
coagulation of nonsolvent
Agarose bioink Fully biological vascular Clinical and biomedical Norotte et al.[67]
tubular grafts, scaffold-free applications
tissue fabrication
Polymer Synthetic Particle reinforcement Graphene/ High electrical con- Nerve tissue engineering, Jakus et al.[29]
composites polylactide-co-glycolide ductivity, mechanically medicine, bioelectronics,
flexible, biocompatible, sensors, and energy devices
neurogenically bioac-
tive, biodegradable, and
surgically friendly
Multiwalled carbon Uniaxial and biaxial Wearable electronics, soft Christ et al.[73]
nanotube/thermoplastic piezoresistive sensors with robotics, and prosthetics
polyurethane cyclic repeatability in both
the axial and transverse
directions
Single-walled carbon Nanocomposite microcoil, Microelectromechanical Lebel et al.[74]
nanotubes/polyurethane complex multidirectional gears and springs, flexible
shapes, UV curing electrical connections,
microprosthetic devices,
tissue engineering scaffolds
Carbon nanotube/epoxy Reduced number of voids High-performance Khater et al.[99]
within epoxy, improved CNT structural applications
dispersion, and adhesion
with epoxy
Hexagonal boron High thermal conductivity, Microelectronic industry Liu et al.[78]
nitride–silver/nanoparticle- excellent alignment along
modified epoxy printing direction
Polyethylene oxide/ Significantly greater thermal Energy storage, wearable Cheng et al.[79]
silane-treated hexagonal conductivity (1.031 W−1 K−1) electronics
boron nitride
Nanoclay/epoxy Flexural strength of up to Filler materials, gas Hmeidat et al.[82]
143 MPa barriers, flame retardants
Silicate/epoxy Multiscale and temporal Electronics, advanced Johnson et al.[83]
morphology, nanoscale biomaterials, and structural
structural alignment applications
Magnetite/epoxy Solved critical matrix–filler Electromagnetic shielding, Restrepo and
interfacial issues, maximum structural construction, Colorado[68]
compressive strength of up and building material
to 200 MPa
Table 1. Continued.

Neodymium–iron–boron/ Substrate-free, remote Flexible electronics, Kim et al.[84]
silica nanoparticles/ magnetic actuation, fully biomedical devices, and
silicone rubber matrix reversible transformation soft robotics
from 2D planar structures
to 3D shapes
Fiber reinforcement Epoxy/silicon carbide Balsa wood inspired, four Energy absorbers, Compton and Lewis[100]
whiskers/carbon fibers times greater strength than catalyst supports, vibration
pure epoxy resin damping, and insulation
Oligomerized bisphenol- High order fiber align- Aerospace, automotive, Lewicki et al.[70]
F diglycidyl ether/ ment, highly orthotropic civil, and energy storage
diethyltoluenediamine/ mechanical and electrical
cyanate ester resin/carbon responses
fiber
Epoxy/carbon fiber High order fiber alignment, Structural applications, Pierson et al.[88]
90% of the theoretical manufactured components
tensile modulus, 66% of the and tooling
theoretical tensile strength
Silicone elastomer/flax Overcame tip clogging Soft robotics, biomedical Jiang et al.[90]
fiber issue using sonication devices, and flexible
process, more than doubled wearable electronics
tensile properties using 0.2
wt% surface-modified flax
fibers
Epoxy/carbon fiber/ Unprecedented high Aerospace, automotive, Nawafleh and Celik[91]
nanoclay compression strength (673 defense, and marine
MPa), flexural strength (401 industries
MPa), flexural stiffness (53
GPa), and fiber volume
ratio (46%)
Epoxy/silicon carbide Acoustic focusing, two- Functionally graded soft Collino et al.[15]
fibers phase ordered structures robots, monolithic and
using a single nozzle lattice composite materials,
and electrical interconnects
Epoxy/carbon fiber Rotational DIW, bioinspired, Structural materials Raney et al.[85]
site-specific optimization
of fiber arrangements,
programmable strain
distribution and failure, and
enhanced damage tolerance
Biopolymer composites Polylactic acid/bioglass/ Increased roughness, Tissue engineering Serra[92]
polyethylene glycol hydrophilicity, excellent and other biomedical
mechanical and bioactive applications
properties
Polylactic acid/ Good biocompatibility, mac- Bone tissue engineering, Zhang et al.[93]
hydroxyapatite roporous, bone repairing graft substitutes in
capacity reconstructive surgery
Beta-tricalcium phosphate/ Higher Young’s modulus Bone tissue engineering Diogo et al.[94]
alginate than the trabecular bone
Polycaprolactone/ Best combination of Electric stimuli for bone Goncalves et al.[101]
hydroxyapatite/carbon mechanical behavior and healing
nanotubes electrical conductivity for 2
wt% carbon nanotubes
Collagen/alginate/silica High porosity (>78%) Hard tissue regeneration Lee et al.[95]
Iron oxide/mesoporous Excellent compressive Local anticancer drug Zhang et al.[96]
bioactive glass/ strength (13–16 MPa) delivery
polycaprolactone
Figure 4. DIW of hydrogels. a) Design of the tree-like 3D-printed living tattoo for chemical detection on human skin (top). Hydrogels with different
colors illustrate the different types of cells encapsulated, the living tattoo on skin in different states (middle): stretched (left), compressed (middle),
and twisted (right), the response of the living tattoo on the skin (bottom) smeared with Rham (left), IPTG (middle), or AHL (right). Reproduced with
permission.[109] Copyright 2017, Wiley-VCH. b) Optical image of a 3D hydrogel scaffold acquired during DIW. Scale bar: 200 µm (left) and optical fluo-
rescence microscopy images of 3T3 fibroblasts plated on the flat glass control. Scale bar: 100 µm (top left), 1D micro-periodic hydrogel scaffold. Scale
bar: 100 µm (top right), and 3D microperiodic hydrogel scaffolds of four layers (bottom left) with a higher magnification view (bottom right). Scale
bar: 20 µm. Reproduced with permission.[111] Copyright 2009, Wiley-VCH. c) An image sequence showing the embedded 3D printing of a branched,
hierarchical vascular network within a compacted embryoid body-based tissue matrix connected to inlet and outlet tubes, seen entering the tissue
from the left and right. Scale bar: 10 mm (first column) and the image of the perfusable tissue construct after 12 h of perfusion (top of the second
column) and fluorescent image of live/dead (green/red) cell viability stains at various sections through the tissue (bottom of the second column). The
DIW caused CNC particles to reorganize from random to par- for sensory devices. For example, Lei et al.[116] created a skin-like
allelly aligned orientations. The nanocellulose molecules also hydrogel, with grid microstructures into a capacitor circuit that
acted as a rheology modifier due to the strong hydrogen bonding responds to external stimuli, i.e., temperature or pressure, since
between the nanocellulose and RSF molecules. Another chal- the volume phase transition can be fine-tuned based on the
lenge faced in hydrogel fabrication using conventional meth- design of the interpenetrating polymer networks. In a parallel-
odologies like colloidal templating or interference lithography plate capacitor, capacitive response can be tailored by changes
at the microscale for tissue engineering is the inability to vary in geometric area of the plates. DIW enabled a sub-millimeter
the spacing between patterned features over length scales from resolution of the conductive layers in the microstructure, which
sub-micrometer to tens of micrometers.[111] Through DIW, enhanced the relative area changes upon stimulation, thus
versatility in structural hierarchies can be achieved in printed magnifying the capacitive response signals. As a result, the
hydrogels, creating more complex architectures and shapes 3D printed hydrogel-based device demonstrated excellent per-
across dimensions. For instance, Wu et al.[113] were able to take formance in sensing body temperature and human motion.
omnidirectional printing a step further by eliminating layer-wise Another application of double networks involved cell encapsu-
patterning and introducing freeform fabrication of chemically lation using a complex microporous architecture that offered
crosslinked photocurable bioinks. exceptional toughness enabled by the combination of covalently
Both chemical and physical crosslinks within the hydrogel crosslinked poly (ethylene glycol) and ionically crosslinked algi-
networks have their respective advantages and limitations. As nate.[117] Collectively, the aforementioned research can lead to
previously discussed, chemical crosslinks provide mechan- the DIW fabrication of unique hydrogel architectures previously
ical strength and structural stability, while physical crosslinks unachievable by standard manufacturing methods through
are generally a weaker form of bonding but provide stim- crosslinking optimization.
uli-responsive and reversible bond formation. Therefore, One of the most enticing applications of hydrogel DIW in
researchers have investigated the application of both types of recent years has been organ printing and tissue regenerations.
crosslinking to maximize their advantages. Combined phys- A wide range of biocompatible hydrogels are viable candidates
ical and chemical crosslinked networks are generally regarded for tissue substitution and have been fabricated using DIW.
as double network hydrogels due to the presence of both stiff Gelatin–methacrylamide is a hydrogel system frequently used
and soft/stretchable components. Chen et al.,[114] for example, in the fabrication of cartilage tissues and other cardiovascular
showed that using different types of cross-linked polymers, applications. Melchels et al.[119] managed to formulate and char-
ionically crosslinked carbomer and covalently cross-linked poly- acterize a bioink of gelatin–methacrylamide through the addi-
acrylamide (PAAm), leads to a tough hydrogel with high Young’s tion of gellan gum and by tailoring salt concentrations. The
modulus due to the combined effect of crosslinking/addition of inclusion of the gellan gum in the ink causes ionic crosslinking
carbomer. Carbomer was used as an optimal rheology modifier that imparts a stable gel-like characteristic. However, a cati-
for the DIW ink that can retain its shape and accuracy until it onic environment is necessary for the gellan gum to form
reaches its fully crosslinked state. The physical crosslinks from the physical networks. The cationic environment in hydrogel
the carbomer help to further strengthen the covalent network precursor is ensured by the presence of salt. As the ink flows
by acting as energy dissipators. Another example of dual-phys- through the nozzle during extrusion, the physical networks
ical crosslinking (DPC) hydrogel was demonstrated by Jiang breakdown under shear. The shear loading is stripped away
et al.[102] They were able to direct-write hydrogels with ultra- when the filament exits the nozzle, and the ionic network rap-
high strength and toughness by building cross-linking DPC idly recovers, resulting in the development of a stable hydrogel
networks based on chitosan (CS) and poly(vinyl alcohol) (PVA). filament. Since ionic interaction causes the gellan chain to
The synergetic interactions of the rigid CS ionic network and form and receive stability, and salt assures a cationic environ-
the ductile PVA crystallization network led to large deforma- ment that favors ionic interaction, salt concentration can also
tions without fracture. Dual-crosslinking design has also been influence the strength of the gel. Thus, the synergetic effects
used by Highley et al.[115] to enable the printing of multimate- of both gellan gum addition and tailoring the salt concentra-
rial structures of supramolecular hydrogels. The noncovalent tions enabled the researchers to print various 3D structures
bonds facilitated the extrusion of the inks into support gels and (hemisphere, hollow cylinder, pyramid) with high cell viability
helped the formation of freeform architectures with open chan- using this bioink. Another group, Billiet et al.[120] fabricated
nels. These double networks have also been shown to be useful artificial liver tissue constructs from gelatin methacrylamide
dashed line represents the equivalent viability depth for an avascular control perfused only from the outside. Scale bar: 1 mm. Reproduced under the
terms of Creative Commons Attribution license.[30] Copyright 2019, AAAS. d) FRESH printed scaffolds with complex internal and external architectures
based on 3D imaging data from whole organs. (i) A dark-field image of an explanted embryonic chick heart. (ii) A 3D image of the 5 d old embryonic
chick heart stained for fibronectin (green), nuclei (blue), and F-actin (red) and imaged with a confocal microscope. (iii) A cross section of the 3D CAD
model of the embryonic heart with complex internal trabeculation based on the confocal imaging data. (iv) A cross section of the 3D printed heart in
fluorescent alginate (green) showing recreation of the internal trabecular structure from the CAD model. (v) A dark-field image of the 3D printed heart
with internal structure visible through the translucent heart wall. (vi) A 3D rendering of a human brain from MRI data processed for FRESH printing.
(vii) A zoomed-in view of the 3D brain model showing the complex, external architecture of the white matter folds. (viii) A lateral view of the brain 3D
printed in alginate showing major anatomical features including the cortex and cerebellum. (ix) A top-down view of the 3D printed brain with black
dye dripped on top to help visualize the white matter folds printed in high fidelity. Scale bars: 1 mm (i and ii) and 1 cm (iv, v, viii, and ix). Reproduced
under the terms of Creative Commons Attribution license.[118] Copyright 2015, AAAS.
using DIW. The cell viability of their printed structures was supported positive tissue infiltration, adipose tissue formation,
found to be 97%, which promotes liver-specific functions such and constructive tissue remodeling. Thus, Pati et al. showed
as glycogen storage and albumin production. By adjusting the that DIW is a promising approach for soft tissue regeneration
printing parameters, including printing temperature, inlet as it facilitates the printing of customized biomimetic tissue
pressure, printing speed, the researchers were able to print analogs. Beyond adipose, lung, and liver tissues, bioengineered
constructs having high shape reliability and desired stiffness. spinal cords have also been fabricated via multimaterial DIW.
These printing parameters correspond to the rheological as well Joung et al.[123] utilized Matrigel-based cell-laden hydrogel inks
as physical aspects of the printing ink, thereby substantially and silicone scaffolds to direct-write stem-cell-derived neural
impacting the final structure of the printed object. Moreover, progenitors for spinal-cord regeneration. Thus, biomimetic,
these parameters control the strut diameter. For example, at hydrogel-based scaffolds have the potential to model complex
the same pressure, the higher the printing speed, the lower central nervous system tissue architectures in vitro and bring-
the strut diameter. On the other hand, at the same printing forth new treatments for neurological diseases and spinal cord
speed, the higher the printing pressure, the greater the strut injuries. However, the low mechanical strength of hydrogels
diameter. Different correlations between printing parameters implied that DIW of self-supporting structures using hydro-
can result in significantly different printed structures and gels remained challenging until the work of Hinton et al.[118]
printing quality. For instance, the diameter of the nozzle is They embedded a printed hydrogel inside a secondary hydrogel
related to the ease with which ink can be extruded for printing. which acted as a temporary, fugitive, thermo-reversible support
The smaller the nozzle diameter, the higher the printing reso- bath. The technique was termed freeform reversible embedding
lution, which results in a relatively smooth surface and more of suspended hydrogels (FRESH). The development of FRESH
precise printing. However, a nozzle with a too small diameter enabled them to foster various types of organ printing from
can result in nozzle clogging and hence, inconsistent extrusion. trabeculated embryonic hearts (Figure 4di–v) to even human
Large nozzle diameter, on the other hand, ensures consistent brains (Figure 4dvi–ix) with reconstructed complex 3D external
extrusion but lacks printing accuracy. Finally, nozzle speed is and internal anatomical architectures. DIW of hydrogels have
also important for high precision printing since too fast a speed also been combined with artificial intelligence (AI)[124] to print
might induce dragging, which can cause the extruded filaments on moving, freeform surfaces.[125] This novel technique has
to break down. Low speed, on the other hand, might induce facilitated DIW structures directly on the back of a free-moving
flow instabilities and excessive printing time. For these reasons, human hand like electronic circuits. Furthermore, the method
it was necessary for the researchers in this work to adjust the has been applied to deliver cell-laden hydrogels to wound beds
printing parameters for developing 3D printed architectures of live mice, which paves the way for future studies on wound-
with high shape reliability and desired stiffness. healing diseases. Overall, DIW of hydrogel inks is crucial for
While Billiet et al. printed liver tissues, Horváth et al.[121] future advancement in new areas of medical treatments like
were the first to print lung tissue analogs. They engineered an tissue regeneration and whole organ printing.
in vitro air–blood barrier with a precise architecture that closely
resembled the physiological microenvironment of native lung
tissues. DIW has also provided an avenue for researchers to 4.1.4. 4D Printing
closely mimic and construct vasculature, a central component
of tissues viability that provides nutrients, growth/signaling, 4D printing of polymers is one of the most novel and inter-
and waste transport. Kolesky et al.[27] reported a new bioprinting esting features of 3D manufacturing. By its definition, 4D
method that overcomes the challenge of direct deposition of printing takes into consideration material deformation and
vasculature into the tissue construct. They used biocompat- change of material properties and/or functionalities over time
ible hydrogel inks composed of Pluronic F127 and GelMA for due to different external stimulus exposure. Typically, the mate-
multi-nozzle printing of the constructs. The final vascular- rials deformation or shape-shifting behaviors in 4D printing
ized, heterogeneous cell-laden tissue construct was found to includes folding, bending, twisting, expansion/contraction, and
have cell viability retention of greater than 95%. Beyond cell curling.[126] 4D-printed materials can be classified depending
viability, another challenging parameter in organ printing on the various stimulus—temperature, pH, humidity, electrical
is cell density. Skylar-Scott et al.[30] overcame the difficulty field, magnetic field, and light. Thermoresponsive polymers
of generating organ-specific tissues with high cell density such as shape-memory polymers regularly have glass transition
(≈200 million cells mL−1) and self-healing capabilities using a temperatures (Tg) superior to their working temperatures.[127]
sacrificial gelatin gel printing method. Moreover, employing These polymers obtain the permanent shape when the tempera-
DIW facilitated the printing of vascular channels (Figure 4c) ture is raised above the glass transition temperature and return
in any arbitrary direction, as seen in nature, by fine-tuning the to their temporary shape once they are cooled. Thus, increasing
tissue matrix composition and bioink rheology. DIW has also and decreasing temperature around Tg causes thermal expan-
enabled the printing of adipose tissue constructs. Pati et al.[122] sion and contraction, and these cyclic changes in temperature
utilized decellularized adipose tissue (DAT) matrix bioink to actuate a printed structure. Similarly, pH can stimulate actua-
direct-write tissues that resemble the human adipose tissue- tion of the printed structure in a solution, and pH-responsive
derived mesenchymal stem cells (hASCs). The precision and hydrogels are highly studied as stimuli-responsive polymers
engineered porosity of the printed structures enabled high in 4D printing.[42] The change of pH of the surrounding media
cell viability over two weeks. The constructs were implanted triggers a structural or chemical change that alters the swelling.
in mice and did not cause chronic inflammation but rather For instance, polyelectrolyte hydrogels have acidic or basic
pendant moieties on the polymer chains that can protonate or structure, they were able to produce orientation gradients in
ionize with a variation of the pH of the surrounding medium, their printed structures perpendicular to the print direction.
which in turn reshapes the molecular chains of the polymer The orientation gradient results in complex deformations via a
and expands the material. The materials which respond to combination of bending and contraction of the same sample.
moisture are called moisture responsive materials. Typically, With this method, they were able to achieve an actuating hollow
hydrogels in an aqueous atmosphere take up water until the cylinder (Figure 5a) capable of lifting 600 times its own weight.
moisture saturation point is reached. Thus, hydrogels permit In another study, Pozo et al.[130] found that temperature can
the enlargement of 200% of their original volume. In the enhance the extent of motion and reverse the direction of light-
case of photoresponsive materials (light-induced stimulation), driven motion. When illuminated at room temperature, the 4D
absorbed light heats up and reconfigures the polymer chains, printed structures bent away from the light source. However,
which causes the relief of strain to induce shape-changing in when illuminated at temperatures above 45 °C, the same actu-
the printed structure. Actuation in printed polymers can also ator bent towards the light.
be achieved via electrical excitation (electroactive materials). On the other hand, hydrogels require enrichment of their
Typically, this involves the displacement of ions during elec- matrix composition with nanoclay (laponite),[134,135] car-
trical stimulation and/or electrostatic force-induced electro- bomers,[114] sugars,[136] or alginate[137] to induce shear-thin-
mechanical changes within the material. 4D-printed polymers ning rheological behavior for proper extrusion. These dopant
that react to magnetic fields are called magneto responsive materials have also been shown to impart additional material
polymers. From the materials perspective, Zhou et al. classified property specializations, including thermal activation,[114,134]
the shape-shifting materials in 4D printing into two subcatego- remote activation,[114,138] and cellular deposition/integration[135]
ries: shape-changing materials and shape-memory materials. A for their intended applications. The key strategy employed by
shape-changing material changes shape gradually when a stim- Cheng et al.,[137] for example, was the introduction of an ionic
ulus is applied and returns to its permanent shape immediately crosslinking network (alginate) into a functional hydrogel pre-
after a stimulus is removed. On the other hand, shape-memory cursor that not only induced shear-thinning but also enhanced
materials follow two-step cycles. In step 1 (programming step), the mechanical toughness of their demonstrated 4D hydrogels.
the structure is deformed from its original shape and held in These structures include a hydraulically controlled artificial ten-
a metastable temporary shape, while in step 2 (recovery step), dril, a pneumatically controlled heart, and a thermally activated
the original shape is recovered with an appropriate stimulus. multimaterial tendril whose radius of curvature was determined
Therefore, shape-memory materials can maintain a tempo- by the thickness of the passive PDMS substrate. McCracken
rary shape until an appropriate stimulus is applied and shape- et al.[135] found a protein-free method to imbed favorable mate-
changing materials cannot. To date, most efforts have been rial properties for long-term selective cellular deposition of
devoted to shape-shifting polymers, including shape-changing biogenic apatite crystals—the main inorganic component of
(liquid crystal elastomers and hydrogels) and shape memory hard biological tissues. This was achieved through selective
polymers showing great prospects in areas ranging from the printing of laponite-functionalized 2-hydroxyethyl methacrylate
biomedical field to soft robotics and space applications. (HEMA)-based hydrogels onto 2D and 3D unmodified HEMA
Liquid crystal elastomers (LCE) have been of recent interest microstructures. Through this method, micro-scaffolding could
for 4D printing applications. Their microstructural composi- be fabricated to induce localized bone reconstruction. Remote
tion allows for large, reversible, and anisotropic shape change activation of a programmed shape change is another desirable
under external stimuli, including temperature,[128,129] light,[130] feature for in situ biological applications. Researchers have
and mechanical shape programming.[131] The reversible actua- found that the addition of ferromagnetic nanoparticles[114,138]
tion depends on the transformation between the nematic and to a hydrogel not only imparts general remote activation capa-
isotropic state at the nematic–isotropic temperature (TNI). LCEs bilities but actuation of the printed structure can be manipu-
exhibit macroscopic contraction or elongation when the tem- lated by nanoparticle orientation within the composite matrix.
perature is above or below TNI, respectively.[132] The liquid crys- Examples are a hydrogel octopus that could “swim” across a
talline phase of elastomers exhibits similar local organization to petri dish under an applied magnetic field[114] and a 4D printed
that of a crystalline material through the orientation of meso- shape changing scaffold that can be used as an intravascular
gens, without long-range positional ordering typically found stent (Figure 5b).[138]
in a crystal structure.[133] These orientation patterns vary from Shape memory effect can be induced in materials through
liquid isotropic phase to nematic and finally smectic phase- the the incorporation of hierarchical architectures. These architec-
most organized phase of a liquid crystal. Alignment of liquid tures can be composed of features, such as hierarchical pores
crystal mesogens into nematic and smectic phases has been or dopant nanoparticle alignment. By gaining control over
demonstrated through two main methods; shear thinning from these scale-dependent features, the macroscale mechanical
ink extrusion[128,130] and incorporation of reactive cross-linkers response of the overall structure, including its deformation,
such as azobenzene.[130] Zhang et al.[129] fabricated single com- strength, and stiffness, can be fine-tuned. Wu et al.[142] studied
ponent liquid crystal elastomer in its isotropic state by DIW the effect of hierarchical and intrastrand porosity on the shape
on a cryogenic platform. The ink was loaded into a steel barrel memory capacity of thermally responsive silicone elastomers.
(syringe), then the temperature was set at 200 °C, and the This was achieved through the addition of “microballoons”—
platform temperature was kept at 10 °C using a temperature pore-forming microspheres—with varying glass transition tem-
controller. By adjusting the temperature differential between perature (Tg) and shell stiffness. They found that the addition
the two sides of the deposited biphenyl-based liquid crystal of lower Tg microballoons not only demonstrated substantial
Figure 5. 4D printing. a) Photograph showing weight-lifting of a printed double-layer strip (0.02 g). Scale bar: 10 mm. Reproduced with permission.[129]
Copyright 2019, American Chemical Society. b) Optical image of the multilayer 4D scaffold printed by c-PLA/Fe3O4 ink (top left) and the detailed struc-
ture of the scaffold (top right), restrictive shape recovery process triggered by a 30 kHz alternating magnetic field at different times (middle), and 4D
scaffold as an intravascular stent where, SD and SRr represent the deformed and recovery shapes under restrictive conditions, respectively (bottom).
Reproduced with permission.[138] Copyright 2017, American Chemical Society. c) SEM micrographs of scratched and healed surface at different scales.
Reproduced with permission.[139] Copyright 2018, American Chemical Society. d) Thermoresponsive uniaxial elongation of gel tubes with alternating
cylindrical discs of active pNIPAM (red) and passive pAAM (green) segments. Optical and FE simulation snapshots of shape change of tube at different
temperatures. Reproduced with permission.[140] Copyright 2019, American Chemical Society. e) CAD/CAM process for automated printing of 3D shape
imitating target tissue or organ through visualized motion program. Reproduced with permission.[141] Copyright 2016, Springer Nature.
compression sets when heated at or above the Tg but could developed in printed hydrogel (PAAm and PNIPAAm) bilayers
attain full structural recovery when reheated. Ko et al.[136] addi- through the addition and subsequent removal of sucrose and
tionally found that macropores significantly improved the glucose. A direct improvement of shape retention was found
response time to thermal stimuli. Uniquely, macropores were with a linear increase in sucrose concentration and higher
swelling ratios were observed with the subsequent increase which is easily metabolizable. However, PLMC has high rigidity
macroporosity. Low temperature thermally expansive mate- at body temperature (37 °C) and degrades too slowly for in vivo
rials have also been functionalized into shape memory. Zhou applications. Kang et al.[141] successfully developed a system
et al.[143] distributed microdroplets of ethanol and liquid metal that improved the mechanical strength of cell-laden hydrogels
throughout a silicone matrix. The low boiling point of ethanol by integrating synthetic biodegradable polymers consisting of
allows for its effective vaporization, expanding the pores leftover three components: composite hydrogel, poly(ε-caprolactone)
by droplet suspensions within the system while the functional- polymer and Pluronic F-127. This not only addressed previous
ized liquid metal (eutectic gallium–indium) droplets improved structure integrity limitations of the underlying hydrogels, but
the mechanical properties of the composite and improved its also allowed for vascularization of the bioprinted specimen
general stability and deformation. (Figure 5e). Print resolution down to 2 and 50 µm was achieved
Besides shape memory transformation, features such as self- for biomaterials and cells, respectively. They detected a com-
healing can also be incorporated into the material composition pound muscle action potential, which was consistent with that
of a 4D printed structure to improve its mechanical longevity. of an immature and developing muscle.
Kuang et al.[139] used UV-assisted DIW of a highly stretchable
semi-interpenetrating polymer network (semi-IPN) elastomer
with an embedded semi-crystalline thermoplastic. The semi- 4.1.5. Food Printing
IPN elastomer manifested shape memory properties during
tensile and compressive testing as well as during cyclic loading. Recently, 3D printing for food materials has been explored
At ambient temperatures, structures of this elastomer were for its potential to create a range of opportunities and ben-
stretched up to 600% strain with in-plane isotropic properties. efits, including food customization with the desired shape
To demonstrate its shape memory characteristics, an object, (Figure 6b), nutrient content and texture, consumer pref-
printed with this material, was stretched at 70 °C, then fixed erences, and the capability to reduce food waste.[38,148–151]
in position at 0 °C, and then returned to its original shape Extrusion-based printing (i.e., DIW) has especially gained
once reheated. Kuang et al. also demonstrated the self-healing prominence in this application due to its ability to accommo-
properties of their semi-IPN. Scratching and notch tests were date various soft food materials. Within extrusion-based food
carried out to demonstrate the healing properties of semi- printing techniques, air pressure-based extrusion is suitable for
IPN under repeated damage in the same locations (Figure 5c). low viscosity materials, while syringe-based extrusion is used
Although present, material scarring was minimal and not vis- for high viscosity and high-strength materials.[152] Researchers
ible to the naked eye. have successfully printed various materials such as mashed
Although most 4D printing research encompasses the devel- potato, chocolate, cheese, and vegetable/fruit puree. For
opment of 3D-to-3D actuation, preprogrammed 2D bilayers to example, Zhang et al.[153] printed dough fortified with prebi-
3D actuation are also considered a variation of 4D printing. otics, useful for innovative cereal-based foods with functional
This form of actuation is typical for most hydrogel-based geo ingredients. The ink was formulated via optimization of flour/
metries. This is partly because overhangs and extreme geometric water ratio, type of flour with cultured protein, and amount of
features are particularly challenging for hydrogels due to their calcium caseinate additive. To obtain the optimal viscosity for
intrinsically low Young’s Modulus and crosslinking density.[144] printing, properties such as moisture content, rheology, and
Researchers have successfully created methods to theoretically thermal behavior are considered and tailored. In addition, it can
model complex biomimetic architectures that actuate from be beneficial to incorporate food additives that act as rheological
hydrogel bilayer composites.[11,145] Specifically, Gladman et al.[11] modifiers.[154] For instance, Liu et al.[155] observed an improve-
found that the print orientation of each fibrous bilayer deter- ment in extrudability and shape retention for mashed potato
mined the deformation swelling mechanisms displayed after formulations supplemented with potato starch. It is important
submersion in water (−45°/45° for twisting, 90°/0° for closing). to note that food printing also may require careful applica-
Other demonstrations of complex architectural actuation of post-processing steps,[152] like baking or pan-frying, to
tion have been prominently directed towards biologically rel- achieve the final edible product (Figure 6c-i–iv). Therefore, con-
evant applications, including the fabrication of tubing[140,146]/ sidering post-processing in addition to printing itself, one main
stents,[147] scaffolding,[147] and artificial muscle.[141] These struc- challenge is maintaining the shape of the printed structure,
tures are printed directly and can transform into secondary or which have so far been addressed with the use of rheological
tertiary structures. Liu et al.[140] theoretically and experimentally modifiers or structural supports.
demonstrated feasible shape changes of tubular structures, Periard et al.[156] constructed the first extrusion-based tech-
including uniaxial elongation, radial expansion, bending, and nique, known as Fab@Home 3d printers, for food materials
gripping in multimaterial prints with approximately 400µm such as butter cookies, turkey with transglutaminase, and
resolution (Figure 5d). The mechanics of these various shape celery fluid gel to make complex designs. In addition to various
changes could potentially be applied at biologically relevant food materials like meat, vegetables/fruits, and bakery items,
diameters (≤ 100 µm)[135] for further improvement in biomed- researchers have also used this technology for food ink with
ical devices like stents. Polymers such as poly(d, l-lactic acid) unconventional ingredients, such as algae and insects, in order
(PLMC)[147] have been considered for self-tightening sutures, to investigate innovative nutrient fortification.[152] For these dif-
and self-expanding scaffolds and stents as shape-changing ferent food material systems, often additives, like agar and gel-
activation have been found to initiate at temperatures slightly atin, are employed to optimize the formulation and printability.
lower than its Tg (45 °C), and PLMC can degrade into lactic acid For example, Wang et al.[157] reported effective printing for
Figure 6. Food printing. a-i) Printing step: close-up of raw chicken being deposited in a square pattern from a food printer. (ii) Cooking step: a blue
laser beam being directed by a set of mirror galvanometers to a raw sample of chicken. Reproduced under the terms of Creative Commons Attribu-
tion license.[159] Copyright 2021, Springer Nature. b) Food design (left) for 3D printing and fabrication sample (right). Reproduced with permission.[150]
Copyright 2015, Elsevier. c) Examples of customized sweets: (i) chocolate (ii) colorful sweets (iii) sugar structures (iv) chocolate rose. Reproduced
with permission.[152] Copyright 2017, Elsevier. d) Optical images of 3D printed structures printed by direct chocolate-based ink 3D printing. Reproduced
under the terms of Creative Commons Attribution license.[43] Copyright 2019, Springer Nature.
surimi gels optimized with a 1.5% w/w NaCl surimi mixture. Blutinger et al.[159] introduced a DIW technique that, for the
Sodium chloride was specifically used to solubilize surimi pro- first time prints, a food material while simultaneously cooking
teins and initiate the protein unfolding to obtain a gel. Mean- the printed structure with the use of a multi-wavelength laser
while, potato starch is a popular rheological modifier due to its cooker (Figure 6a-i,ii). The multiwavelength laser ensures food-
excellent water retention properties, transparency, and aging safe cooking temperatures and comprises a high-powered diode
properties. In fact, Yang et al.[158] printed lemon juice gel with laser, along with a set of galvanometers. This novel single-step
added 15% w/w of potato starch. Yet most popularly, DIW has DIW and cooking technology enable more design freedom and
been employed for chocolate printing. DIW, particularly hot- less cooking loss. Ultimately, DIW offers great versatility and
melt extrusion, has been utilized for chocolate printing. How- exciting possibility for the future of food.
ever, recently, Karyappa et al.[43] were able to overcome the major
challenge of needing temperature control by using varied choc-
olate materials to tailor ink formulation rheology (Figure 6d). 4.2. DIW of Ceramic-Based Structures
Along with chocolate syrup and paste, high concentrations of
cocoa powders (up to 25%) in inks exhibited shear-thinning Ceramics, typically consisting of oxides, nitrides, and carbides,
properties at room temperature. Moreover, advanced DIW tech- are popular due to their high strength, thermal stability, bio-
niques, such as laser-assisted food printing, have shown great logical compatibility, electrical insulation, and exceptional
capability in overcoming current challenges, including sim- resistance to abrasion and corrosion.[160] These materials are
plification in postprocessing steps like cooking, boiling, and finding widespread technological application in structural,
baking. Utilizing a simple ink formulation of blended chicken, electrical, photonic, and biomedical sectors. Many of these
applications require complex architectures with features that ranged from 134 to 157 MPa. On the other hand, Rosental and
span multiple length scales ranging from several micrometers Magdassi[166] replaced the organic additives with inorganic
to millimeters. However, conventional ceramic manufacturing barium titanate (BTO) sol–gel precursors, which resulted in
processes, including injection molding, die pressing, and tape increased solid loading while maintaining printability. The
or gel casting, are limited in generating complex structures.[161] final printed structures were nearly fully dense (97.8% of the-
Furthermore, due to their inherent brittleness, hardness, and oretical density) with nominal 1 wt% organic material con-
high melting temperature,[162,163] defects such as cracking and tent. High solid loading zirconia paste (60 vol%) was used by
thermal gradients arise during the traditional processing of Yu et al.[167] for direct writing of dense structures with a high
these ceramics, leading to poor performance and structural relative density ≈98.1%. Micro-CT imaging has shown that
failure.[164] Conventional techniques are also plagued with DIW was capable of fabricating zirconia parts with very low
longer processing times. AM has emerged as a powerful solu- porosity. The flexural strength, fracture toughness, compressive
tion to existing manufacturing limitations. Among the AM strength, and Vickers hardness of the additively manufactured
techniques, light-based printing techniques (e.g., SLA and parts are 488.96 ± 79.84 MPa, 2.63 ± 0.2 MPa m1/2, 1.56 GPa,
DLP), powder bed fusion techniques (e.g., SLS), and extrusion- and 11.52 ± 0.57 GPa, respectively. While DIW allows engi-
based techniques (e.g., FFF and DIW) have been commonly neering the precursor ink, it also facilitates formulating new
adopted for creating ceramic structures.[161] However, DIW ena- inks such as hydrogel-based inks for creating dense ceramic
bles a far simpler, cheaper, and faster manufacturing process, structures. Feilden et al.[163] and M’Barki et al.[41] employed ther-
specifically compared to other printing techniques. Using DIW, mally reversible hydrogel-based inks containing -Al2O3 and an
it is possible to fabricate freestanding ceramic structures with Al2O3 precursor (boehmite), respectively, for assembling dense
high-aspect-ratio walls without the need for supports, which is ceramic struts. Both inks were supported by van der Waals
not possible with other 3D printing techniques. A great range interactions and formed an interconnected gel-like network
of complex ceramic structures can be created using this tech- that displayed the desired viscoelastic ink rheology. Remarkably,
nique, from dense monolithic parts to porous scaffolds and M’Barki et al. were able to maintain near-full theoretical density
ceramic matrix composites (CMCs). ≈ 97% for the final structure with a significantly higher flexural
strength of up to 600 MPa—more than four times than that of
Rueshloff.[41]
4.2.1. Ceramic Oxides Although minimization of porosity is necessary for
forming dense structures, it may not always be a detrimental
DIW has been used for the production of 3D objects composed feature. Mainly, in biomedical applications, like ceramic
of a variety of oxide ceramics such as alumina (Al2O3), titanium scaffolds, porosity plays a significant role in the effective
oxide (TiO2), zirconia (ZrO2), yttria-stabilized zirconia (YSZ), nutrient exchange and regeneration of tissues by facilitating
yttrium-aluminum-garnet (YAG), barium titanate (BTO), etc. cell seeding, penetration, and distribution. For example, Li
These materials typically possess impressive properties such as et al.[168] demonstrated the ability of DIW in creating 3D scaf-
high melting point, low wear resistance, and improved water/ folds with precise control of their internal architecture. 3D
chemical resistance. As a result, they are used for various pur- cylindrical and woodpile ZrO2 porous scaffolds with a porosity
poses, including materials and chemical processing, radiofre- of more than 50% were fabricated, which showed compres-
quency and microwave applications, electrical and high voltage sive strength in the range of 8–10 MPa. 3D porous internal
power applications, and foundry and metal processing. architecture was found to be beneficial for HCT116 cell growth
Dense structures comprising oxide ceramics are attractive by providing more locations for cells attachments and prolif-
due to their better mechanical strength compared to porous eration. Although DIW had enabled the fabrication of highly
structures. Successful fabrication of dense structures requires porous ceramic structures, achieving hierarchical porous
minimization of porosity. However, obtaining a dense and com- ceramics has remained a technological challenge. DIW has
plex structure from these ceramics has been challenging. The recently been combined with various foam processing tech-
feedstock in conventional AM techniques typically consists of niques, such as particle-stabilized foaming, freeze casting,[169]
high organic (binder) and low ceramic content (solid loading), emulsion templating,[24] biological foaming,[170] and more,[171]
and removal of the organic contents during heating and/or to achieve hierarchical porous structures. These structures
sintering may leave uncontrolled porosity and cracks in the (having porosities at multiple length scales) outperform their
printed structure. Furthermore, the conventional techniques nonhierarchical counterparts regarding relative compressive
generally involve high-energy light sources or high-tempera- strength as well as the accessibility of the active surface of the
ture extrusion, which results in thermal gradients in the final material.[172,173] Muth et al.[25] reported bioinspired, lightweight,
printed structure. However, DIW provides a viable method of and hierarchically porous ceramic structures created from
manufacturing that confirms nearly full densification because particle-stabilized foams. The structures possessed hexagonal
of its room temperature extrusion and the freedom of tailoring and triangular honeycomb cellular geometries to enable the
the organic/ceramic loading in the precursor ink. For example, final ceramic form to exhibit multiple modes of deformation
Reuschhoff et al.[165] fabricated near-net-shaped dense ceramic and greater specific stiffness [>107 Pa (kg/m3)−1]. Furthermore,
components via room-temperature direct writing of highly simple variation in the architecture (e.g., unit cell type and strut
loaded aqueous alumina (Al2O3) suspensions. At 58 vol% alu- porosity) enabled systematic tuning of the elastic modulus
mina loading, they achieved a maximum average bulk density of the created structures (≈1 GPa for hexagonal honeycombs
of 98.2% for the sintered samples, while the flexural strength composed of foam struts to 27 GPa for triangular honeycombs
composed of nearly dense struts). Moon et al.[169] fabricated gas industry, valves, seals, rotating parts, wear plates, location
ceramic scaffolds with porous filaments by combining DIW pins for projection welding, cutting tooltips, abrasive powder
and freeze casting. Frozen alumina/camphene suspensions blast nozzles, metal forming tooling, etc. DIW has shown great
were extruded into cellular structures and subsequently promise in terms of rapidly fabricating complex 3D structures
freeze-dried, resulting in a macroporous alumina scaffold from nonoxide ceramics having dense struts as well as those
with interconnected and elongated pores within the filaments. with controlled porosity.
However, this approach led mainly to open porous aniso- Engineering the DIW ink with high loading of ceramic sus-
tropic structures and poor bonding between extrusion lines. pension is a common route for fabricating dense struts. Cos-
As an alternative method that could address these limitations takis et al.[178] printed boron carbide (B4C) structures using
and cover a wider range of pore sizes, porosities, and pore- a suspension of highly loaded (56 vol%) B4C in a polyethyl-
morphologies, Minas et al.[24] proposed a novel and versatile eneimine (PEI) solution to ensure particle stability by steric
approach for the fabrication of hierarchical porous ceramics repulsion. Increasing loading content, however, was found
(Al2O3) based on the combination of DIW and emulsion/foam to increase warping in the final specimen due to anisotropic
templating (Figure 7a). While the millimeter-sized pores are shrinkage. The optimal solution that ensured shape retention
simply controlled through the distance between the printing with no observable warpage was found to be at 54 vol% B4C in
lines (mesh size) during DIW, micron-sized macropores are 25 000 g mol−1 of PEI. While the low density and high melting
determined by the emulsification process parameters, thus point (≈2450 °C) of boron carbide make it an attractive mate-
achieving a range of pore sizes facilitated by the combination rial for harsh environmental applications, the high flexural
approach. The resulting hierarchical porous Al2O3 scaffolds strength, specific stiffness, thermal insensitivity, and electrical
showed remarkably high relative compressive strength. DIW properties of SiC make it ideal for high voltage electronics and
has also been combined with biological foaming (BF) by Jin high-temperature sensors. Cai et al.[179] printed 3D silicon car-
et al.[170] to develop Si2N2O ceramic foam. They achieved supe- bide (SiC) parts using concentrated, aqueous colloidal ink con-
rior printing behavior using inks consisting of ceramic powder sisting of SiC, Al2O3, and Y2O3 particles in a dilute polymer
and yeast suspensions. The mechanical properties, evolution solution with a total solids volume fraction of 0.44 via DIW, fol-
of phases, and pore density of the ceramic parts were found lowed by low-pressure spark plasma sintering (SPS) to achieve
to be affected by the variation of yeast contents. The Si2N2O dense ceramic bodies. The final samples displayed above
foams with porosities from 61.5 ± 4.3% to 71.0 ± 4.5% were suc- 97% of theoretical density, showing ≈22.8% linear shrinkage
cessfully fabricated with corresponding compressive strength from green to sintered state. While Cai et al. combined SPS
of 33.1 ± 2.6 and 8.3 ± 1.5 MPa. This study by Jin et al. provided with DIW in order to achieve dense structures, Zhao et al.,[180]
a reference for the preparation and printing of BF ceramic ink showed that DIW combined with sintering and hot isostatic
and hierarchical ceramic foam using DIW. Combining sacri- pressing can provide a viable manufacturing approach to create
ficial templating with DIW, Arango et al.[174] synthesized mul- dense Si3N4 implants with controllable shape and architecture.
tiscale porous TiO2 foams that can be 3D printed into planar, Since it is difficult dispersing Si3N4 powders in aqueous media
free-standing, and spanning hierarchical structures. They to high solids loading, a cationic polyelectrolyte, polyethylen-
were able to tune the rheological properties and foam micro- imine (PEI), was used as a dispersant-binder system. Four-
structure (i.e., open- or closed-cell) by varying the foam-inks’ point bending tests of as-fabricated dense beams showed a
composition and frothing conditions. Additionally, the foams’ flexural strength of 552 ± 68 MPa. Another non-oxide ceramic
functional performance (photocatalytic in this case) was found is SiOC, known for its mechanical strength and chemical sta-
to be correlated with their microstructure, improving for bility. Dense and complex SiOC structures were achieved by
open-cell architectures. Another important porous architec- Huang et al.[162] They derived two dense SiOC origami ceramic
ture, aerogel structures from silica inks has been developed structures through DIW of a two-part silicone elastomer. They
by Zhao et al.[175] They were able to formulate a dilute silica followed two approaches: filament-assisted origami and self-
nanoparticle suspension (sol) that could be extruded to print adhesive origami, to fold the as printed 2D patterns into 3D
miniaturized mesoporous sol–gel materials. After printing, structures (Figure 7b). Uniquely, no additional reinforcement
the silica sol is gelled in an ammonia atmosphere to enable materials (i.e., nanoparticles) were needed for structural rein-
subsequent processing into aerogels. These silica-based aero- forcement. Secondary shaping using origami of different 2D
gels displayed excellent mechanical properties, high specific layers with varied designs allowed the manufacturing of spiral,
area, and ultralow thermal conductivity, useful for applications flower-like, and polyhedron architectures, which are difficult
related to thermal management. to fabricate without adding supports or by any conventional
ceramic fabrication processes.
DIW offers the freedom of printing porous structures
4.2.2. Ceramic Nonoxides from non-oxide ceramics. Elsayed et al.[181] reported DIW of a
porous ceramic based on a Ti2AlC, a MAX phase ceramic pos-
Nonoxide ceramics such as boron carbide (B4C), silicon nitride sessing unique properties that are intermediate between those
(Si3N4), silicon carbide (SiC), silicon oxycarbide (SiOC), tita- of ceramics and metals. Ti2AlC inks with appropriate rheology
nium aluminum carbide (Ti2AlC) has excellent wear and corro- were developed by dispersing Ti2AlC powders in a water-based
sion resistance properties, even at high temperature and severe solution containing organic binders. Ti2AlC lattices with con-
thermal shock conditions. These types of ceramics find their trolled porosity (in the range of 44–63 vol%) were manufactured
application in various sectors such as pharmaceuticals, oil, and using DIW, and these lattices showed a very high compressive
Figure 7. DIW of ceramics. a) Processing schematics of hierarchical porous ceramics prepared by emulsion/foam templating and DIW with rheological
modification through gelation (route I) or emulsification/foaming (routes II and III), a cubic lattice scaffold (bottom left) and an emulsion templated
structure (second from the left to the last at the bottom) with closed porosity (42 vol% Al2O3 and 0.04 mmol g−1 propionic acid). Reproduced with
permission.[24] Copyright 2016, Wiley-VCH. b) SiOC samples with complex architecture from 3D printing and origami technique (first two rows from the
top) and folded 3D hexahedron (third row) and flower-like structures (fourth row). Reproduced with permission.[162] Copyright 2020, Elsevier. c) Flow
chart of the custom bone defects repair (first two rows) and representative optical images of surgical operation for implantation with scaffolds (third
row), Reproduced with permission.[176] Copyright 2013, SAGE Publications. d) 3D printing of microsupercapacitors (MSCs) with interdigital architec-
tures (top left), optical image of the MSC device printed on a glass substrate before drying (top right), excellent adhesion of the printed devices to
the substrate during repeated bending and twisting (middle row), cross-sectional SEM images of the electrodes in the MSC device (bottom left), and
MSC device printed on glass and polymer substrates (bottom right). Reproduced with permission.[177] Copyright 2020, American Chemical Society.
strength (89–43 MPa). Sesso et al.[182] fabricated hierarchical printed structures. On the other hand, sub-millimeter scale
porous ultra-high temperature ceramics (zirconium diboride, porosity was achieved with the addition of oil into the pre-
ZrB2) with a high strength to density ratio. The ink used in this cursor ink and micron-scale porosity was obtained in the scaf-
work was a capillary suspension containing interpenetrating fold filaments during sintering. Such materials could be used
networks of oil and water phase. Millimeter scale porosity was as insulation near very high-temperature surfaces in aerospace
achieved via controlling the inter-filament distances in the applications.
4.2.3. Bioceramics convert into ceramics. Zocca et al.[188] printed highly porous
(≈80%) hardystonite bio-ceramic foam and reticulated scaf-
Bioceramics, such as calcium silicate (wollastonite), calcium folding by heating preceramic polymers and precursor fillers.
zinc silicate (hardystonite), calcium phosphate (tricalcium Printed structures possessed good mechanical properties,
phosphate, hydroxyapatite) are utilized in biomedical fields, with bending strength of 136 ± 4 MPa and fracture toughness
particularly bone tissue generation, because of high stiffness, of 1.24 ± 0.03 MPa m1/2 for samples with a relative density of
biocompatibility, and osteoconductivity. Among different AM 83 ± 3%. Elsayed et al.[189] improved further these structures
methods, DIW has gained attention for printing bioceramics through the addition of embedded SrO, MgO, and glass fillers
due to its ability to build up the structure on any surface (Ca1.4Sr0.6Zn0.85Mg0.15Si2O7). As a result, strong scaffolds
without any masking, tooling, or the requirement of a powder were obtained with increased biocompatibility, bioactivity, and
bed and expensive laser sources. Furthermore, the technique compressive strengths (>12 MPa). The densification and the
allows one to control the porosity in the final printed structure, integrity of cellular scaffolds were enhanced by using fine glass
which is crucial for biomedical engineering applications. powders as additional fillers that improved the mechanical
Common bioceramics of the calcium phosphate family, properties of the Sr/Mg-doped hardystonite ceramic.
including hydroxyapatite, tricalcium phosphate, biphasic Over the past two decades, increasing attention has been
phosphate, are popular because of their use as bone damage given to the calcium silicate-based bioceramics such as wol-
replacement and implantable material. DIW using concen- lastonite (CaSiO3) and diopside (CaMgSi2O6) as a potential
trated colloidal inks offers a new approach for creating 3D peri- biomaterial for bone repair due to their appreciable bioac-
odic hydroxyapatite (HA) scaffolds. By carefully tailoring ink tivity. Researchers have exploited the benefits of DIW in devel-
composition and viscoelasticity, HA scaffolds can be built with oping ordered macroporosity and homogenous micro-porosity
minimal organic content (≈1% by weight) without the need for simultaneously in the struts to fabricate calcium silicate-based
sacrificial support material or mold. Michna et al.[183] reported bioceramic scaffolds. Elsayed et al.[190] demonstrated the fab-
direct-write assembly of HA scaffolds comprised of self-sup- rication of wollastonite-diopside bioceramic scaffolds by DIW
porting cylindrical filaments (or rods) patterned with varying of an ink based on a silicone preceramic polymer and fillers.
lattice constant. By tailoring their printed architecture and sin- They found that the addition of glass powder to the ink ena-
tering conditions, HA scaffolds were created with a bimodal bled the fabrication of 3D printed scaffolds with high strength
pore size distribution, consisting of an interpenetrating 3D net- (≈8 MPa for a porosity of 67 vol%). Shen et al.[191] also fabricated
work of large pores between HA rods (characteristic diameter wollastonite-diopside biphasic bio-ceramic scaffolds with core–
of ≈200–500 µm) and finer micropores (<1 µm) within the HA shell structure. In this case, foreign doping ions such as zinc
rods. Simon et al.[184] printed 3D periodic scaffolds composed (Zn), strontium (Sr), and organic porogen were added into the
of micro-porous HA rods arrayed to produce macro-pores that powder slurry. It was found that the Zn- or Sr-doping aided in
are size-matched to the trabecular bone of rabbits. It was shown adjusting the mechanical strength of the scaffolds. Meanwhile,
that the printed scaffolds with controlled multiscale porosity, due to the addition of the organic porogen, the controllable
when implanted in the trephine defects of skeletally mature high-density micropores could be introduced into the shell
rabbits, led to rapid bone formation and growth within eight layer after sintering, which helped in tuning the biodegradable
weeks. Tricalcium phosphate bio-ceramics exhibit a higher bio- properties of bioceramic scaffolds. Ke et al.[192] fabricated highly
degradability (higher resorption rate) than hydroxyapatite. Tovar bioactive Wollastonite scaffolds and then modified with magne-
et al.[185] has printed beta-tricalcium phosphate (TCP) material sium (Mg) doping for pore-wall reinforcement. The modified
scaffold successfully with the help of DIW for repairing crit- scaffolds demonstrated better compressive strength than the
ical-sized long-bone defects of white rabbits. The custom-engi- unmodified ones while being favorable for retarding biodissolu-
neered beta-TCP scaffolds were resorbable, biocompatible, and tion and mechanical decay of scaffolds in vitro. In-vivo investi-
able to directionally remodel and regenerate the bones while gation showed that the modified scaffolds displayed limited bio-
maintaining decent mechanical properties. Miranda et al.[186] degradation, accelerated new bone ingrowth (4–12 weeks), and
fabricated hard tissue scaffolds made of β-TCP (β-Tricalcium elicited a suitable mechanical response. Shao et al.[176] observed
phosphate) using the DIW technique. However, to overcome a similar effect when they printed Mg-doped wollastonite scaf-
nonuniform drying during writing, the deposition was carried folds as a custom repair of a mandibular alveolar bone defect
out in oil. In their follow-up work, Miranda et al.[187] studied in a rabbit (Figure 7c). The printed scaffolds exhibited a mild
and compared the mechanical behavior under compressive in vitro bio-dissolution with moderate weight loss of ≈7%, a
stresses of β-tricalcium phosphate (β-TCP) and hydroxyapatite considerable initial flexural strength (31 MPa), and significant
(HA) scaffolds fabricated by DIW. Both scaffolds were found to osteogenic capability.
exhibit excellent mechanical performances in terms of strength
(68 ± 12 MPa for HA and 27 ± 9 for β-TCP).
Hardystonite ceramics have been demonstrated to be condu- 4.2.4. MXene
cive to both osteoblast-like cells and osteoclasts, suggesting their
potential use for skeletal tissue regeneration and as coatings. Ceramic-based 2D atomically thin materials, MXenes, have
One way of obtaining these ceramics is through the pyrolysis recently received significant attention from the scientific com-
of polymeric precursors under inert atmospheres at tempera- munity. These materials consist of thin layers of transition
tures above 800 °C. Using DIW, the preceramic polymer-based metal nitrides, carbonitrides, or carbides. MXenes combine
ink can be extruded into complex shapes and then heated to their hydrophilic surface functionalities (OH, F, and O)
with the metallic conductivity of transition metal carbides, and other fields[197–200] due to their excellent high-temperature
making them desirable for several applications.[193] Another performance and low density. Traditional technologies to fab-
critical advantage of MXenes over other functional materials ricate CMCs include gel-casting, compression molding, fiber
is that they can form aqueous and organic inks without the weaving, etc. However, these processes were unable to produce
need for any additional additives. As a result, researchers have customized parts and complex structures required for specific
attempted to print MXenes using DIW.[32] Zhang et al.[194] uti- applications.[201] Although CMCs had already been developed
lized this property to formulate 2D titanium carbide (Ti3C2Tx) by other AM routes,[202–204] engineering the precursor mate-
MXene inks in an aqueous and organic solvent. They were rial (ink) with effective reinforcements and intricate freeform
able to direct-write conductive tracks, micro-supercapacitors, design flexibility remained a challenge. Feilden et al.[205] uti-
and ohmic resistors on paper substrates. The high electrical lized DIW to print dense CMCs using short carbon fibers as
conductivity and pseudocapacitive behavior of MXenes com- reinforcement and investigated various ceramic matrix sys-
bined with the spatial uniformity and high printing resolution tems, including SiC, Al2O3, and SiC-B4C. However, at high
of DIW resulted in order of magnitude increases in volumetric sintering temperatures, cracks were found in the CMCs, either
capacitance and energy density. However, the conductivity of due to the reaction between fibers and oxides or due to thermal
3D printed MXene structures depends strongly on the orienta- expansion mismatch. The first ink suitable for the direct-
tion of MXene flakes.[32] Orangi et al.[177] showed that the orien- writing of complex-shaped CMCs was developed by Franchin
tation of MXene flakes in the printed Ti3C2Tx structures can be et al.[206] They utilized the unique formability of preceramic
controlled by adjusting the printing parameters and ink char- polymers to develop an ink containing chopped carbon fibers to
acteristics of DIW (Figure 7d). This could be another possible fabricate a CMC component with complex shape, high porosity
route towards improving the electrical properties of DIW fabri- (≈75%), and good compressive strength (≈4 MPa). They were
cated MXene devices. able to produce CMCs with optimized mechanical and micro-
Yang et al.[195] showed that MXene platelets with a high structural properties to align high aspect ratio fillers along the
aspect ratio increased the viscosity even at low concentrations printing direction. However, the printed structures using this
and thus facilitated the printability of the ink. They formulated CMC ink were not able to fully withstand their own weight and
viscoelastic inks of 2D Ti3C2Tx with a relatively large lateral size showed significant deformation in the self-weight direction.
(≈8 µm). The 3D printing process and the post-printing freeze- Another issue was the use of silica as an additive in their ink
drying approach resulted in the assembly of 2D flakes into a which limits their high-temperature applications. To solve these
porous architecture within the filaments and prevented the two issues, in their follow-up work, Franchin et al.[207] devel-
normal restacking of the flakes. As a result, the surface area oped a new ink formulation that did not use silica and ensured
of the printed structures improved significantly compared to that the printed structures better retained their shapes due to
conventional techniques (e.g., casting or vacuum filtration). the appropriate rheology of the ink. They printed single fila-
Printed energy storage devices with high specific areas demon- ments with this ink that showed a mean flexural strength above
strated excellent performance, including high capacitance and 30 MPa. They observed non-catastrophic failure with contin-
energy density. This work shows that DIW of MXene inks can uous deformation, also known as a graceful failure mode.
be extended to the printing of high-performance functional and Despite these advances, the juxtaposition of material prop-
structural materials in various industries. In another study, Yu erties like toughness and strength in ceramic composites
et al.[196] developed crumpled nitrogen-doped MXene (MXene- complicates the optimization of manufacturing parameters,
N) nanosheets via melamine-formaldehyde templating method including structure size, complexity, and manufacturing time.
to address the challenge of restacking of the 2D sheets, which However, natural structures, such as crustacean shells, provide
typically reduce the electrochemical performance of the devices. blueprints to overcome this. These natural structural materials
In this way, they not only prevented MXene nanosheets from have complex, hierarchical architectures designed to control
restacking but also doped nitrogen into MXene frameworks, crack propagation and fracture. Feilden et al.[211] utilized DIW
which ultimately resulted in commendable device performance. to print bioinspired ceramic-based composite parts, possessing
Overall, DIW of MXene-based devices can be central to the microstructures unattainable by traditional production tech-
advent of flexible electronics and supercapacitor-based energy niques. Their printed components contained a high-volume
storage devices. Although the MXene family currently con- fraction of ceramic material, similar to natural materials. They
sists of about 30 compounds, only Ti3C2Tx inks for DIW have fabricated highly mineralized ceramic/polymer composites
been formulated so far. Therefore, it is highly anticipated that based on aligned alumina platelets with microscopic Bouli-
formulating viscoelastic inks to optimize the printability of gand structures that guided crack propagation and twisting in
other MXenes can be a promising research direction to open a three dimensions. Thus, they were able to retain strength while
myriad of potentially untapped applications. enhancing the toughness by altering the fracture behavior on
a mechanistic level in their microscopic ceramic architectures.
Such designs of new printable materials with controllable
4.2.5. Ceramic Composites mechanical characteristics have also advanced in recent years
due to the alliance between nanotechnology and 3D printing.
Ceramic matrix composites (CMCs) have great potential for Specific designs of nanoscale building blocks have facilitated
applications in various fields such as aircraft (combustion cham- engineered materials with specifically tuned macroscopic
bers, turbine blades), aerospace (aircraft surface heat shields, behavior. Domènech et al.[208] used a direct-write self-assembly
rocket nozzles), military (nose cones and missile nozzles), technique to construct free-standing, millimeter-scale columns
Figure 8. DIW of ceramic composites. a) DIW of colloidal assembly for CMC fabrication performed by dispensing the colloidal suspension from a
high-precision needle, followed by the controlled downward motion of the substrate and syringe plunger. This allows the construction of free-standing
mm-sized columns such as the one presented in the digital photograph (bottom row, left). High-resolution SEM images of the cross-section of one
column revealing the ordered arrangement of nanoparticles and grain boundaries between the micron-sized supercrystalline grains. Reproduced
with permission.[208] Copyright 2020, Wiley-VCH. b) DIW of Al2O3-GO composite and printed objects in the form of cylinders and micropillars (left
column). 3D printed cylinder made with Al2O3 platelets/GO paste after sintering at 1550 °C (right column). Reproduced with permission.[209] Copyright
2017, American Chemical Society. c) 3D ink extrusion of a polystyrene-based SnO2-7% CuO ink followed by sintering and liquid metal infiltration (left)
and microstructure of Ag-52 vol% SnO2 composite produced by pressureless Ag infiltration (right). Reproduced with permission.[210] Copyright 2020,
Elsevier.
comprising 15 nm diameter spherical iron oxide nanoparticles demonstrated that the addition of less than 0.1 wt% of graphene
(NPs), surface-functionalized with oleic acid (OA). The process oxide (GO) reduced shrinkage and improved structural sta-
schematic is shown in Figure 8a. The structures self-assembled bility during firing. The GO fillers lost their oxygen functional
into face-centered cubic (FCC) super crystals within minutes groups during firing, thus inducing electrical conductivity into
during the direct-writing process. The subsequent crosslinking the composite. García-Tuñón et al.[209] utilized GO and ceramic
of OA molecules resulted in nanocomposites with elastic mod- particles in an aqueous paste without any additive to facilitate
ulus up to 58 GPa and maximum strength of 110 MPa, as high the DIW of ceramic (SiC and Al2O3) composites (Figure 8b).
as newly engineered platelet-based nanocomposites. They showed that the GO simultaneously played the role of
Beyond the improvement of mechanical properties of a rheology modifier, binder, and dispersant. This work also
ceramic composites, DIW can also aid in the development of paved the way for DIW of several other graphene-based ceramic
functional ceramic components. This was achieved mainly by composites.[213] SnO2–Ag composite structures also have great
incorporating graphene or metallic conductive reinforcements potential in producing functional materials for electrical appli-
into the ceramic precursor ink. Pierin et al.[212] fabricated elec- cations. However, the densification of SnO2 nanoparticles into
trically conductive SiOC composite parts using DIW. They bulk parts is challenging due to the poor sintering capacity of
SnO2. DIW alleviates this difficulty as densification is achieved Targeted towards biomedical applications, bioactive glasses
during the heat treatment into near-equilibrium microstruc- have been of interest due to the ability of AM to fine-tune
tures with minimal residual stresses. Therefore, Chen et al.[210] architectural features, such as porosity, that are crucial to
printed SnO2 with complex architecture by DIW and then infil- improving compatibility and performance of biomedical struc-
trated the structure with molten Ag, forming a ceramic com- tures and devices, such as scaffolds. In particular, bioactive
posite with interpenetrating designed architectures (Figure 8c). glasses have beneficial properties, including the ability to sup-
The resulting composites showed good structural stability and port the growth of bone cells, strong bonding among the tis-
preserved high conductivity upon thermal shock cycles between sues, and the capability to adjust to its degradation rate with
850 °C and 20 °C. Thus, DIW has enabled the fabrication of bone repair and growth process.[217] Deliormanli et al. created
both mechanically stable and electrically conductive complex- silicate (13-93) and borate (13-93B3) bioactive glass scaffolds
shaped ceramic composites to be used in structural as well as that had a compressive strength of 142 ± 20 MPa and 65 ±
electrical applications (Table 2). 11 MPa, respectively, values far higher than that for trabecular
bone.[218] Liu et al.[219] produced a silicate (13-93) scaffold (86 ±
9 MPa) from a water-based solvent utilizing polymeric binder
4.3. DIW of Glass-Based Structures Pluronic F-127. Other hydrophilic polymeric binders have also
been used to fabricate bioactive glasses via DIW, including
Glass, an amorphous solid, is a widely used material because ethylcellulose/polyethylene glycol and carboxymethyl cellu-
of its optical properties, insulation, durability, hardness, and lose. However, unlike Pluronic F-127, these binders rely on
chemical and thermal stability. Consequently, various glass- processing in ethanol which reduces premature ionic release
based structures have been successfully developed using AM beneficial to bone regeneration.[220] Pluronic F-127 hydrogel-
techniques such as molten filaments and laser-aided filament- based suspensions ensured good stability for the ink rheology,
fed processes. However, some of these techniques require were strong enough to keep the glass particles in suspension
precise control of temperature and high expense to ensure and facilitated glass printing.[214] Consequently, the researchers
structural stability.[214] DIW, on the other hand, has proved to successfully printed a scaffold with 45S5 bioactive glass by
be a more feasible technique to obtain broader compositions as mimicking nature’s porous bone structure and performance.
well as higher design freedom for glass-based structures with The printed scaffold had a compressive strength of 136 MPa
controlled resolution and properties. at 60% porosity which is much higher than previously printed
One of the main properties critical to glass applications is glass and ceramic scaffolds.[221] Unlike previous studies, the
transparency. Previous printing attempts, for example, via printed glass had less than 50% silica, which acted as network
binder jetting, presented limitations, including fragility and formers. Lower network connectivity was observed to further
opaqueness due to incomplete densification.[215] DIW addressed enhance the dissolution rate and bioactivity. Based on this
these limitations by demonstrating that transparent, free-form observation, Nommeots-Nomm et al.[220] investigated if bioac-
glasses in 3D geometries with sub-millimeter features could tive glass-based scaffold—PSrBG and ICIE16—, containing
be formed,[215] as shown in Figure 9a-i,ii. This process involves less than 50 mol% silica respectively, could be printed via DIW
the printing of a suspension of hydrophilic fumed silica nano- following the similar aqueous Pluronic-F127 ink formulation.
particles in tetraglyme, along with the addition of PDMS. Fur- The formulation proved successful in providing the right ink
thermore, unlike conventional glass manufacturing techniques, rheology, therefore, demonstrating that Pluronic F-127 can be
the process does not require high temperatures during printing used as a universal binder regardless of glass reactivity. More-
and forms a structure that prevents cracking during drying. A over, Nan et al.[214] observed that Pluronic F-127 had an ionic
variety of hierarchical structures were created including face- strength insensitivity that led to good ink rheology and sta-
centered tetragonal as well as the first-ever 3D-printed micro- bility for water-sensitive glass materials like borosilicate. The
fluidic cross junction with 400 µm wide channels, as described researchers printed micron-sized borosilicate glass with high
by Nguyen et al.[215] Destino et al.[216] combined DIW with con- alkali and alkaline oxide contents in Pluronic-F127. Overall,
ventional glass thermal processing methods to convert a sol-gel DIW, with the aid of Pluronic-F127, addressed the challenge
derived silica and silica–titania colloidal feedstocks into optical of hydrolyzation of alkaline earth and alkali oxides in water-
quality glasses. Printable silica and silica–titania sol inks were based ink systems, known for negatively impacting the ink
prepared directly from molecular precursors by a simple one- rheology.[214]
pot method, which is optimized to yield shear-thinning col-
loidal suspensions with tuned rheology ideal for DIW. After
printing, the parts were dried and sintered under optimized 4.4. DIW of Cement-Based Structures
thermal conditions to ensure complete organic removal and
uniform densification without crystallization. The printed parts Cement is one of the most widely utilized materials in struc-
had properties equivalent to commercial optical fused silica and tural and/or construction applications. AM techniques, such
silica–titania glasses. The silica inks that were used in these as “concrete printing”[222] and “contour printing,”[223] had been
studies are of general interest to researchers due to their resist- adapted for the construction of large cement-based structures.
ance to thermal shock and the production of dense and trans- However, producing cement-based structures with engineered
parent structures.[214] Thus DIW is potentially on the verge of mechanical responses would require microscale high-resolu-
adding new dimensions to the glass manufacturing industry tion printing. DIW’s high degree of control and flexibility offer
through silica ink printing. high-resolution printing of cement with complex geometries.
Table 2. Summary of the recent progress in DIW of ceramics and ceramic composites.
Classification Material Key features Potential applications Refs.

Ceramics Ceramic oxides Alumina Multilayered near-net shaped dense Lightweight structures, energy Reuschhoff et al.[165]
structure with > 98% of true density and storage devices, and catalytic
high flexural strength (134–157 MPa) applications
Barium titanate Replaced organic additives with an Optical, mechanical, and electrical Rosental and
inorganic sol–gel precursor for a printed devices Magdassi[166]
structure with a density up to 97.8 wt%
with an extremely low organic content
(≈1 wt%)
Zirconium oxide Superior flexural strength (488.96 ± 79.84 Manufacturing, energy storage, and Yu et al.[167]
MPa), compressive strength (1.56 GPa), biomedical industries
and Vickers hardness (11.52 ± 0.57 GPa)
than their conventional counterparts
Boehmite Shape fidelity > 90% and flexural strength Thermoset printed circuit boards M’Barki et al.[41]
(500–600 MPa) with a density up to 97% and catalytic converters
Zirconium oxide Interconnected porous architecture Biomedical scaffolds, biomaterials, Li et al.[168]
with uniform grain size and excellent and tissue engineering
compressive strength (8 and 10 MPa
for 63% and 55% of sample porosity,
respectively)
Alumina Interconnected macroporous and aligned Biomimetic macro/microporous Moon et al.[169]
microporous biocompatible scaffolds architectures, bone tissue
with negligible cytotoxicity and increased engineering, bone scaffolds, and
compressive strength (29.3 ± 7.6 MPa) biomedical applications
Alumina Hierarchical macroporous ceramics with Lightweight structures, biomedical Minas et al.[24]
unprecedented compressive strength of scaffolds, energy storage devices,
16 MPa and 8 MPa for 88% and 93% of and catalytic applications
sample porosity, respectively
Silicon nitride oxide Biological foaming facilitated hierarchical Adsorption and catalytic Jin et al.[170]
ceramics structures with a porosity applications
ranging between 61.5 ± 4.3% to 71.0 ± 4.5%
and corresponding compressive strength
ranging 33.1 ± 2.6 MPa to 8.3 ± 1.5 MPa
Alumina Hexagonal and triangular honeycomb Lightweight structures, tissue Muth et al.[25]
cellular geometries of greater specific scaffolds, thermal insulation,
stiffness (>107 Pa (kg/m3)−1) and high electrodes, and catalyst supports
elastic modulus (≈1 GPa for hexagonal
and 27 GPa for triangular geometries)
Titanium oxide Hierarchically ordered planar, free- Water purification, biomedicine, Arango et al.[174]
standing, and spanning structures with energy harvesting, optoelectronics,
tunable microstructures semiconductors, photocatalysis
application, and waste
management
Ceramic Non-oxides Boron carbide Optimum suspension for DIW is 54 vol% High wear components, light- Costakis et al.[178]
B4C in 25 000 g mol−1 of weight armor, and control rods
polyethylenimine nuclear reactors
Silicon carbide Structures with average grain size 1–2 Microelectromechanical systems, Cai et al.[179]
µm and above 97% of theoretical density, aerospace parts, high-temperature
showing ≈22.8% linear shrinkage reactors, advanced friction systems,
sensors, high power, and high-
frequency devices, and actuators
Silicon nitride Solid samples with a flexural strength of Spinal fusion surgery, bearings in Zhao et al.[180]
552 ± 68 MPa, macroporous (56.5%) grid- knee joint and hip arthroplasty,
like architecture with a flexural strength of dental implants, orthopedic and
89 ± 11 MPa dental surgery
Silicone oxy-carbide Complete shape-retaining spiral, Photocatalytic, biological, and Huang et al.[162]
polyhedron, and flower-like architectures electromagnetic applications
with no pores or cracks
Table 2. Continued.

Titanium aluminum Increased porosity (from 44 vol% to 63 Electrical and high thermal shock Elsayed et al.[181]
carbide vol%) with excellent compressive strength resistant devices
(43–89 MPa)
Zirconium diboride Structural porosity ranging between 71.5% Insulator for high-temperature Sesso et al.[182]
to 83.5% with characteristic strength aerospace applications
of 3.58 MPa (ranging between 0.97 to
10.4 MPa) and Weibull modulus of 2.05
Bio-ceramics Hydroxyapatite Scaffolds with bimodal porous Biomedical implants, bone tissue Michna et al.[183]
architecture and minimal organic content engineering
(≈1 wt%)
Hydroxyapatite Optimal strategy for bone repairing by Biomedical scaffolds Simon et al.[184]
microporous (<1 µm) HA rods
Beta-tri calcium Bone remodeling with porous scaffold Bioactive scaffolds, bone recon- Tovar et al.[185]
phosphate of high tensile (14.76 ± 5 N) and flexural struction, and defects repairing
(11.42 ± 8 N) strength
Beta-tri calcium Structure with controlled roughness and Bone tissue engineering, Miranda et al.[186]
phosphate microporosity orthopedic applications, biomedical
implants, and scaffolds
Hydroxyapatite and Excellent mechanical strength Bone tissue engineering, Miranda et al.[187]
beta-tri calcium (68 ± 12 MPa for HA and 27 ± 9 for β-TCP) orthopedic applications, and
phosphate load-bearing scaffolds
Hardystonite Porous (≈80%) architecture up to a mean Non-load-bearing biomechanical Zocca et al.[188]
compressive strength of 2.5 MPa applications
Sr/Mg-doped Nonstochastic porous architecture with Bioactive scaffolds and biomedical Elsayed et al.[189]
hardystonite a compressive strength of 11.6 ± 3.2 MPa applications
for a total porosity of 48% ± 1% and a true
density of 3.1 ± 0.01 g cm−3
Wollastonite-diopside Porous sinter-crystallized ceramics Bone tissue engineering and Elsayed et al.[190]
with specific compressive strength > biomechanical applications
7 MPa cm3 g−1 (40% increase compared to
other samples)
Zn/Sr doped Porous architecture with limited strength Bone repair and bone regenerative Shen et al.[191]
Wollastonite-diopside decay and favorable bioactive ion release medicine applications
in bioceramic composites
Mg-doped High compressive strength > 20 MPa Bone implants, clinical treatment of Ke et al.[192]
wollastonite with over 60% porosity large bone defects, and bone tissue
regeneration
Mg-doped Considerable initial flexural strength (31 Bone reconstruction and Shao et al.[176]
wollastonite MPa) and significant osteogenic capability regeneration
MXene Ti3C2Tx Energy density up to 32 × 10–4 Wh m−2 Microsupercapacitors, ohmic Zhang et al.[194]
and volumetric capacitance as high as resistors, and conductive tracks
562 × 106 F m−3
Ti3C2Tx Aerial capacitance of 10.35 × 103 F m−2 at Electronic devices, antennas, Orangi et al.[177]
2 × 10–3 V s−1 and an energy density up to sensors, biomedical applications,
51.7 × 10–2 Wh cm−2 and electromagnetic shielding
Ti3C2Tx Areal capacitance of 21 × 103 F m−2 at Electrochemical energy storage Yang et al.[195]
17 A m−2 and energy density up to devices, electromagnetic shielding,
24.4 × 10–2 Wh m−2, gravimetric catalyst, advanced composite
capacitance of 242.5 F g−1 at 0.2 A g−1, and manufacturing, and
power density of 6.4 W m−2 at 43 A m−2 environmental cleaning
Nitrogen-doped Areal capacitance of 82 × 103 F m−2, Micro supercapacitors and Yu et al.[196]

Ti3C2Tx volumetric energy density of 830 Wh m−3, sodium-ion batteries
and areal energy density of 4.2 Wh m−2
Table 2. Continued.

Ceramic composites Silicon carbide, Dense bodies at high sintering tempera- Low-end structural applications Feilden et al.[205]
alumina, and silicon ture, cracks due to thermal expansion
carbide–boron car-
bide (carbon fiber)
Silicone oxy-carbide Structures with aligned fibers in the extru- Instance templating the grain Franchin et al.[206]
(carbon fiber) sion direction exhibited a compressive growth in ceramic parts
strength of ≈4 MPa and porosity of ≈75%.
Silicone oxy-carbide Good adhesion to carbon fibers with Pads and disk brakes for high-end Franchin et al.[207]
(carbon fiber) excellent flexural strength for thinner (31.7 cars
± 6.8 MPa) and thicker (36.4 ± 4.5 MPa)
filaments
Alumina (epoxy) Bioinspired highly mineralized tough Light-weight composites for aero- Feilden et al.[211]
ceramic scaffolds with Bouligand space, aeronautics, and automotive
architectures industry, biomedical implants
Iron oxide (oleic acid) Cross-linked columns with elastic mod- Novel macroscopic architectures, Domènech et al.[208]
ulus between 8 to 58 GPa and bending multifunctional 3D structures,
strength between 39 to110 MPa in absence and mechanically strong
of shear stress transfer mechanism nanocomposite
Silicone oxy-carbide Porous ceramic scaffolds of 3.1 ± 6.8 MPa Lithium-ion batteries, biomedical Pierin et al.[212]
compression strength at 0.1 wt% GO components, porous structures for
content filtration
Silicon carbide and Al2O3 structures with a porosity of 60% Complex 3D ceramic García-Tuñón et al.[209]
alumina and SiC bars with a density of 3.21 g cm−3
as well as bending strengths of ≈212 MPa
Stannic oxide Retained conductivity upon thermal shock, Electron-transporting layers for Chen et al.[210]
cycled between 850 and 20 °C ohmic contacts, low-voltage elec-
trical contacts, battery anodes, and
electric circuits
Consequently, DIW of cement-based materials has gained (micro-CT). This study provided insight into structural aspects,
increasing interest in recent years.[224–227] including processing-induced heterogeneous patterns, interfa-
Cement-based structures are intrinsically brittle. In order cial regions, and pore network distributions for the architec-
to improve the toughness, research efforts have focused on tural patterns.
eliminating the interfaces in 3D printed structures, which Researchers have also attempted to incorporate additives
are known to have detrimental effects on mechanical proper- such as Kaolin,[227] short fibers,[225] and nanoclay[228] to the pre-
ties.[228–232] Moini et al.[224] utilizes DIW technique to harness cursor cement ink to modify the rheology and build structures
the heterogeneous interfaces in cementitious structure by having better mechanical properties. Using Kaolin, a superplas-
employing bioinspired Bouligand architectures. These architec- ticizer based on cellulose and calcium carbonate as additive and
tures are found to generate unique damage tolerance mecha- modifier for the precursor ink, Vergara and Colorado obtained
nisms and allow a unique load-displacement response of the structures having a good degree of geometric stability while
brittle cement-based materials. The various 3D-printed archi- flowing through the extrusion system.[227] However, they noted
tectures of hardened cement paste (hcp) used in their study are that further improvements are required in the compressive
presented in Figure 9b-i. In the study, the compliant structure strength of structures built with this ink. In a different study,
with honeycomb architecture was subjected to cycling loading, Hambach et al.[225] reported DIW of a composite of Portland
and it showed bilinear stress–strain behavior with two distinct cement paste and reinforcing short fibers (carbon, glass, and
moduli of elasticity. Furthermore, they showed that heteroge- basalt fibers, 3–6 mm), which exhibit a unique combination of
neous interfaces improved the overall performance; they led to strength and materials efficiency. They introduced a method of
an increased deflection and enhanced work of failure by over extruding cement paste through a nozzle that aligns 60–70% of
50% (compared to cast counterparts) (Figure 9b-i). Thus, the the fibers in the structure. They found that the alignment of the
architected structures through DIW introduced the possibility fibers along the print path direction led to a flexural strength of
of customizable stress–strain behavior, which is not attainable up to 120 MPa for samples with 3 vol% aligned carbon fibers.
in cast elements. However, further investigation of the micro- Sajadi et al.[228] have developed a nanoclay modified cement-
structures of DIW architectures was required for a proper based ink that enables high-resolution (micrometer scale) 3D
understanding of these mechanisms. In their follow-up work, printing of complex architected structures. To demonstrate
Moini et al.[233] investigated the microstructures of DIW printed DIW of cellular architectures using the modified cement ink,
lamellar architectures using microcomputed X-ray tomography they printed and analyzed different architected topologies:
Figure 9. DIW of glass, cement, and graphene-based structures. a-i) Glass 3D-printing process including ink extrusion from the nozzle (scale bar:
500 µm), printing with the desired geometry (scale bar: 5 mm), ink drying, and silica powder densification at high temperatures to form a transparent,
3D-printed glass part (from left to right), (ii) Solid, monolithic cylinder (20 wt% silica ink) with a scale bar of 5 mm (top left), cup containing dyed
water (top right), woodpile scaffold (bottom left), and scanning electron microscopy of woodpile scaffold with a scale bar of 250 µm (bottom right),
Reproduced with permission.[215] Copyright 2017, Wiley-VCH. b-i) Modulus of rupture (MOR) versus relative density for cement based Bouligand
architectures with varying pitch angles (8°, 15°, 30°, 45°, 90°) and percentages of infill (60% and 100%) compared to MOR of cast control disks (top
row) and compliant structure with honeycomb architecture, cellular sandwich panel prism with solid top and bottom layers, Bouligand architecture
with pitch angles γ = 2° and 45° (from left to right at the bottom row). Reproduced with permission.[224] Copyright 2018, Wiley-VCH. (ii) 3D-printed
cement-based hexagonal honeycomb structure from different perspectives with a scale bar of 10 mm (first two rows of the left column), resolution of
honeycombs with hexagonal, triangular, and star cells and Hil- of GO sheets, they used holey graphene oxide (hGO) for DIW
bert curves (Figure 9b-ii). The higher toughness observed in the (Figure 9c-i). They developed a 3D printed hGO based struc-
printed structures was a combined effect of the architecture, ture with enhanced porosity distribution, which was used as a
fabrication process, and nanoscale additive. Furthermore, the cathode for lithium-oxygen (Li-O2) battery. In their study, they
use of nanoscale additives in the cement ink led to cement set were also able to fabricate complex architectures by stacking
acceleration, potentially leading to faster printing of cement- multiple hGO layers to form freestanding 3D mesh structures
based complex 3D printed structures. Rapid manufacturing of with trimodal porosity. The attainment of such hierarchical
cementitious structures through DIW can have broad applica- porosity (Figure 9c-i) in the printed structure aided in the fab-
tions in civil construction, thermal insulation, and construction rication of energy storage devices with superior electrochemical
products in the energy industry. response. For example, the micro to macroscale porosity in the
printed Li-O2 cathode increased the mass/ionic transportation
and exhibited 63-fold and 42-fold enhancement of the full dis-
4.5. DIW of Graphene-Based Structures charge capacity by area and mass, respectively (Figure 9c-ii,iii).
Although it is possible to formulate binder-free GO-based
The properties of graphene, such as superior mechanical prop- inks, physical and chemical crosslinking by adding different
erties, chemical stability, large specific surface area, and high types of binders and rheology modifiers such as Pluronic F-127,
thermal and electrical conductivity, are not only ideal as a rein- hydroxyl propyl methylcellulose (HPCM), silica, different ionic
forcement material for 3D structures but have reinvented the binders, etc.,[21,240,241] improves the connectivity of the GO
industrial uses of graphene beyond that of battery electrodes, to sheets within the solvent. This consequently strengthens the
sensors, supercapacitors, and catalysis.[36] Therefore, an associa- structural bonding and promotes gelation[242] while improving
tion of DIW and graphene-based material printing can unfold the printability as well as the mechanical strength of the
a great potential in low-cost manufacturing applications. How- printed structures.[243] An efficient cross-linking technique was
ever, pristine graphene cannot be transformed into printable presented by Jiang et al.[244] where they transformed the GO
ink due to strong Van der Waals forces of attraction between sol into a hydrogel by adding a trivial amount of CaCl2 (which
the individual atomic layers that impede their dispersion in served as a gelling/cross-linking agent). The hydrogel exhibited
an aqueous solution or other common solvents. One solution an increase of yield stress and storage modulus by one order of
to the problem is the addition of polymeric binders that can magnitude and prevented structural collapse while maintaining
enhance the printability of graphene slurries. However, intro- the shear thinning flow behavior. In their study, they printed the
ducing such binders can block the active surface area of the water-based GO ink directly at room temperature to fabricate
printed structures that will deteriorate electrical properties and electrodes for supercapacitors. The printed structure is then
functionalities.[235] Although this issue can also be resolved by chemically reduced by hydroiodic acid (HI) followed by thermal
introducing conductive binders such as poly (styrene sulfonate), treatment at 3000 K. The post-treatment provided the struc-
poly (3,4-ethylene dioxythiophene), their number is limited.[236] ture with a stable and conductive graphene network, resulting
Oxidizing graphene to form GO has demonstrated a greater in an outstanding electrical conductivity of ≈ 800 S m−1. The
degree of dispersion in aqueous solutions,[237] and thus, most structure also exhibited remarkable resilience when subjected
research on DIW of graphene-based geometries has utilized to compression. Such enhanced electrical and mechanical
GO as the precursor material for printing. Since GO is not a properties are generated from the coordination interaction or
good conductor, the printed GO-based structures are typically cross-linking among different functional groups in GO ink due
reduced via thermal or chemical treatment to reduced graphene to Ca2+ ions. A similar degree of cross-linking can also be real-
oxide (rGO) to obtain structures with good electrical conduc- ized for other metallic agents such as Al3+,[245] Mg2+,[246] Fe3+,[247]
tivity. Naficy et al.[238] investigated the viscoelastic properties of etc. Besides metallic cross-linking agents, cellulosic materials
GO dispersed in water for various industrial processes such as can also provide structural stability/rigidity to graphene-based
dry spinning and gel-extrusion printing. They considered large structures. Yao et al.,[248] for example, 3D printed graphene-
GO sheets with a high aspect ratio for the formulation of the ink based pseudocapacitive electrodes, in which the ink was an
and reported that the rheological characteristics of GO-based aqueous GO suspension modified with HPCM. However, for
ink depend on the dispersion concentration. This enabled them achieving an outstanding pseudocapacitive performance, MnO2
to prepare stable inks from pristine GO without incorporating was electrodeposited on the printed structure. The 3D printed
any additives. Similar formulations of the GO-based binder- graphene aerogel/MnO2 electrode can simultaneously achieve
free inks had also been discussed by Lacey et al.[239] Instead excellent capacitance normalized to the area, gravimetry, and
printing a honeycomb structure in the z direction (third row of the left column), Hilbert curve with a scale bar of 1 mm (first row of the middle column),
honeycomb structures with triangular cells with a scale bar of 10 mm (second row of the middle column), honeycomb structures with star cells with
a scale bar of 10 mm (third row of the middle column), microscopic view of the section of the Hilbert curve with a scale bar of 500 µm (first row of
the right column), node in the triangle pattern with a scale bar of 500 µm (second row of the right column), and thickness of the printed line in the
star pattern with a scale bar of 500 µm (third row of the right column). Reproduced with permission.[228] Copyright 2019, Wiley-VCH. c-i) Components
(hGO, H2O) used to create the aqueous and additive-free 3D printable ink (first three columns of the top row) and the creation of an aqueous and
additive-free 3D printable hGO ink for extruding complex 3D architectures with hierarchical porosity (macro → micro → nanoscale) (rest of the figure
in given sequence), (ii) Deep discharge performance of the r-hGO mesh, and (iii) Controlled discharge charge cycling depths (1 mA h cm−2) for the
r-hGO mesh (at 0.1 mA cm−2). Reproduced with permission.[234] Copyright 2018, Wiley-VCH.
volume. These findings validate the new concept of “printing” of sufficient electron and ion transport paths and increased
practically feasible pseudocapacitor electrodes and devices. the areal capacitances at considerable degrees of mass loading.
To diversify the advantages of DIW printed graphene-based Such an improvement finds an enormous potential of the aero-
structures, researchers have incorporated cellular or porous gels for energy storage applications, fuel cells, seawater desali-
architectures to extend the range of mechanical, thermal, and nation as well as next-generation micro to nanoscale intricate
electrical properties of the final structure. One example is the hybrid architectural electronics.
development of 3D printed graphene aerogel, which recently While graphene and GO sheets have been printed earlier, the
has got significant attention due to their intrinsic lightweight, controlled assembly of graphite (hundreds of graphene layers)
high porosity, surface area, and their myriad potential appli- into tailored 3D architectures via DIW was not reported until
cations, including biomedical scaffolds, sensors, and super- the recent work of Sajadi et al.[254] The biggest challenge of
capacitors. However, stochastic porous networks in the aerog- printing hundreds of layers of graphene is maintaining print
raphene framework suffer from limited mass transport and continuity and preventing particle jamming during extrusion.
low mechanical strength with significant attenuation in other Sajadi et al.[254] provided a solution to overcome this limita-
physiochemical properties compared to pristine graphene. To tion. They formulated a nanoclay modified graphite-based
overcome this problem, Zhu et al.[249] developed a new GO ink. The nanoclay easily adapted into the graphite layers and
ink and adopted the DIW technique to fabricate the periodic improved the storage modulus. The printed structures had
aerographene micro-lattices into an isooctane (2,2,4-trimeth- excellent thermal, electrical, and mechanical properties, and the
ylpentane) bath. They applied both the gelation and cross- clay additive did not alter these properties due to the excellent
linking methods for the formulation of the ink. The printability inter-layer dispersion and mixing within the graphite material.
is further improved by introducing silica filler that acted as a The DIW of complex graphitic architectures (≈97% graphite)
removable rheological modifier and brought the key rheological without further heat treatments could lead to easy shape engi-
features in good agreement with the properties of the printable neering and related applications of graphite such as circuits
colloidal ink.[250] Such a modification of GO precursor suspen- and heater elements.
sion resulted in a successful printing of the periodic aerogra-
phene microlattices that exhibited superior properties than that
of bulk materials. For example, their study showed that the 4.6. DIW of Metal-Based Structures
macroscale pores incorporated in a periodic pattern lowered
the density and enabled faster mass transport while exhibiting Mainstream 3D printing technologies for metals include selec-
superior mechanical properties compared to their bulk coun- tive laser melting (SLM), electron beam melting (EBM), laser
terpart. However, their electrical conductivity was not sufficient engineered net shaping (LENS), and SLS. These processes typi-
for energy-related applications such as batteries or supercapaci- cally involve a high-energy beam to sinter powder. However,
tors. To improve the conductivity, GO precursor suspension these techniques require an inert environment, especially for
needed further modification. Thus in their subsequent study, active metals, such as titanium, magnesium, and their alloys.
Zhu et al.[251] added graphene nanoplatelets (GNP) with the GO Due to the high-energy beam system and stringent environ-
ink since GNP offers low electrical resistance. The added GNP mental conditions, printing equipment and corresponding
and silica filler contributed to the rheological development of maintenance costs are high. Another disadvantage is the
the ink to a greater extent than that of silica filler alone. In requirement of expensive spherical powders. To overcome
their study, they printed a macroporous electrode for a micro these shortcomings, DIW has evolved as a promising technique
supercapacitor with a power density greater than 4 kW kg−1 that to manufacture 3D metallic structures.
exceeded the conventional devices by a considerable margin.
Thus, the controlled use of GNP in the GO precursor suspen-
sion had made the electrical properties of aerogel sufficient for 4.6.1. Single Component Metal
energy applications. One key feature for both studies is that
they both considered high concentration GO inks for their Compared to ceramics and polymers, printing of complex
printing. However, high GO concentration-based inks are single-metal structures has been challenging due to signifi-
highly susceptible to nonhomogeneity. Moreover, both studies cant post-processing steps (i.e., heat treatment or hot isostatic
considered silica filler as a rheological modifier that is removed pressing), difficulty in finding compatible metals as well as slow
afterward by the chemical etching of hydrofluoric acid. Such build rates, and high expense. However, recent advances in 3D
harsh additive removal may hamper the physiochemical prop- printing have shown that single-metal structures fabricated via
erties of the printed components.[252] Tang et al.[253] had over- DIW can have excellent properties and functional applications
come these limitations and printed hybrid graphene aerogels ranging from electronics to biomedical. One key benefit of this
by DIW. They prepared a gel-like hybrid ink whose rheology technique is customizable geometry, which plays a critical role
was tuned by urea. Urea, in this study, imparted a liquid-like in the complexity of metallic structures. Ahn et al.[23] demon-
response to the ink and developed the strength and elasticity strated that liquid-based TiH2 ink suspensions could be printed
of the printed gel over an order of magnitude. They also dem- via DIW into 2D planar lattice sheets that could be then folded
onstrated the printing of nonplanar geometries on the curved and cut into novel 3D structures (Figure 10a-ii), as inspired by
surfaces and printed hybrid aerogel-based ultrathick electrodes the traditional paper art called origami. Along with geometry,
for microsupercapacitors. Highly coordinated networks within porosity is also crucial, particularly for biomedical applications.
their structural framework had contributed to the development Kleger et al.,[255] for example, used a salt-leaching technique to
Figure 10. DIW of metal-based structures. a-i) Schematic of the laser-DIW printhead, consisting of the laser microscope, silver ink syringe, and nozzle
(left), side view of a freeform 3D printing of a metal hemispherical spiral (top right), and printed butterflies. Scale bar: 1 mm. (bottom right). Repro-
duced with permission.[262] Copyright 2016, National Academy of Sciences. (ii) Optical image of DIW of a concentrated TiH2 ink (top left), SEM images
of printed wavy patterns (bottom left), schematic illustration of rolling procedure for high aspect ratio, cylindrical coils (top right), and SEM images
of concentric cylindrical TiH2 coils without and with a titanium tubular insert (middle left and middle), helix (middle right), stents (bottom left and
print porous scaffolds with magnesium (Mg). Mg is a desired standard manufacturing methods. Incorporating porosity in
implant/scaffold material with similar mechanical properties single-metal hierarchical structures can be challenging, espe-
as bone and promotes bone formation due to biodegradability cially if the metal is brittle and stiff. AM generally employs
and bioresorption properties. However, Mg poses serious chal- cellular structures involving struts or walls that optimize the
lenges for AM due to its high reactivity. Kleger et al. were able mechanical behavior of the metallic structure. In the case of
to develop Mg structures with ordered porosity by combining stiff metals like tungsten (W), however, the contact points due
the salt-leaching process with DIW. They also tune the pores to struts and walls act as stress concentrators, leading to brit-
in the range from submillimeter to the macroscopic scale. tleness at ambient temperature and poor stability. To mitigate
Meanwhile, even smaller, customizable nanoscale pores these issues, Kenel et al.[261] explored the use of gyroid struc-
(10–100 nm)[256] were obtained for printed single-metal structures from WO3 nanopowder-based inks that avoid contact lines
tures by another leaching process called chemical dealloying, in and sharp angles between walls. These porous structures offer
which the most chemically active phase in the parent alloy is greater stability, particularly higher energy absorption—nearly
selectively removed via corrosion. 30 times that of lattice structures at elevated temperatures and
Other processing steps have also been adopted during DIW symmetric stiffness at low densities. These structures realized
to obtain novel single-metal structures. In particular, thermal via DIW can be applicable to interesting applications, such as
postprocessing involves transforming printed green bodies into heat-exchanger with continuous fluid flow as well as complex
a single as well as binary metallic alloy structures through reduc- and lightweight applications (i.e., X-ray collimators and filters
tion and sintering in an Ar/H2 atmosphere at elevated tempera- for high energy X-ray applications).
tures. Generally, the metallic particles are mixed with a polymer Even with simplified and efficient techniques such as
to formulate an extrudable ink, which is then printed into desired leaching and thermal reduction, processing of single-metal
shape and size. The printed structure is then heated at high DIW structures can still be time-consuming and costly.
temperature to burn the polymer away and sinter the metallic Therefore, more recently, researchers have modified the DIW
particles. By utilizing this process, one can reduce warping or printing method itself. One such advanced printing technique
cracking, maintain features ranging from millimeter- to cen- is the laser-assisted DIW[262] that involves a focused laser rapidly
timeter-scale lengths with high aspect ratios, develop multima- heating the deposited ink spots during printing (Figure 10a-i).
terial structures with complex architectures. According to Jakus Remarkably, this process not only allows for the fabrication
et al.,[257] DIW in conjunction with thermal reduction proved of intricate architectures but also reduces the current pro-
to be more efficient than traditional methods to obtain com- cessing and cost. Skylar-Scott et al.[262] applied this method to
plex architectures with a wider range of single-metals (16 types print planar and freestanding 3D metallic curvilinear archi-
including Sn, Al, Ti, Zr, and Zn) as well as single-metal mixtures tectures using silver-nanoparticle ink. The printed structures
(8 types including Zr–Sn–Fe). However, thermal reduction intro- have tunable mechanical and functional properties, including
duced random porosity. Hence, the DIW technique was modified higher thermal conductivity (≈50-fold higher than as-printed),
by incorporation of space holders to allow higher control over the lower electrical resistivity (≈5.4 × 10−6 Ω cm) than bulk silver
geometrical features, such as size and shape,[258] of the pores. (≈1.6 × 10−6 Ω cm), and higher ductility. Overall, the use of
This greater degree of freedom in controlling porosity is signifi- hybrid DIW techniques can introduce exciting avenues to create
cant as it overcomes intrinsic AM printing resolution limitations. complex hierarchical structures with unique properties and
Xu et al.[259,260] developed solvent-cast-based DIW for metal to materials without the need for further postprocessing steps.
fabricate dense metallic structures by combining a room temper-
ature 3D printing and subsequent heat-treatments: sintering and
secondary metallic infiltration. In order to improve mechanical 4.6.2. Metal Alloys
properties and electrical conductivity, as-printed structures were
infiltrated by copper after sintering. Young’s modulus of fabri- As DIW is a low-cost, highly customizable, and rapid manu-
cated structures is up to 195 GPa and approaches typical values facturing process, there has been much interest in its applica-
for similar bulk material. On the other hand, the conductivity is tions towards printing fully dense metallic architectures with
1.42 × 106 S m−1, which is superior to the structures fabricated by optimized mechanical performance. Researchers have used
most commercial 3D printing techniques.[259] many different approaches to tailor the mechanical proper-
DIW proved to be successful in creating open-porosity ties of these metallic structures, including adjusting thermal
hierarchical metallic complex structures, not achievable via processing,[181,266] modifying the manufacturing process,[267]
middle), and square latticed hollow cylinders (bottom right). (Scale bar: 2 mm). Reproduced with permission.[23] Copyright 2010, Wiley-VCH. b) Printing
the ink into a microlattice with 200 µm diameter struts, coreduction, interdiffusion, and sintering of the powders in the green body to yield a CoCrFeNi
HEA micro-lattice (left). Scale bars are 3 mm, and microstructural evolution of 3D extrusion printed CoCrFeNi HEA filaments (right). Cross-section
of a 3D extruded filament (top), filament sintered at 1173 K for 1 h (middle) and CoCrFeNi HEA filament sintered at 1573 K for 20 min (bottom). Scale
bars are 25 µm for low magnification and 3 µm for high magnification micrographs. Reproduced under the terms of Creative Commons Attribution
license.[263] Copyright 2019, Springer Nature. c-i) Schematic illustrations of each step of reconfiguration (top to bottom of the first column), schematic
illustration of the micro-LED array with reconfigured 3D interconnects (top right), and colorized SEM image of the micro-LED (blue) array, and EGaIn
(yellow) interconnects. Scale bar: 300 µm (bottom right). Reproduced under the terms of Creative Commons Attribution license.[264] Copyright 2019,
AAAS. (ii) Soft sensing skin measuring the finger flexion/extension connected by an electroless nickel immersion gold (ENIG) finished flexible flat
cable (FFC) (top left), soft sensing skin attached on the fingers using medical tapes, with the FFC connected to the customized PCB (top right), sensor
signals recorded during finger motion (bottom). Reproduced with permission.[265] Copyright 2019, American Chemical Society.
fabricating complex macroscale architectures,[261,266,268] and stress shielding. Elsayed et al.[181] utilized DIW to print highly
tuning porosity.[181,269] porous (up to 65 vol%) and equiaxed grain Ti6Al4V scaffolds
One emerging approach for the fabrication of metal alloys by employing high vacuum and sintering time and tempera-
is electrodeposition-based DIW. Researchers commonly inves- ture (1450 °C for 3 h). The printed structures have higher com-
tigate copper alloys for enhanced electrical and thermal con- pression strength than those produced by energy deposition
ductivity applications such as thermocouples, thermopiles, and AM techniques. On the other hand, Song et al.[269] produced
heat flux sensors. Wang et al.[267] fabricated single-phase solid titanium metal-matrix composites Ti-B2, Ti-B, and Ti-C with
solution nanocrystalline (<35 nm) Cu–Ni alloys with varying increased compressive strength for porosities ranging from
compositions from a single electrolyte using electrodeposition- 24% to 77%. A resulting surface roughness of ≈1 µm was also
based DIW. By incorporating electrodeposition into the 3D found to be ideal for osseointegration.
printing process, the researchers aimed to enhance the thermal The novelty of high entropy alloys (HEA) has also been of
stability and magnetic properties of the printed structure great interest to AM researchers. Primarily, studies have applied
through the creation of a high purity nanocrystalline alloy. Elec- high-energy AM techniques such as powder bed fusion, selec-
trodeposition also promotes interlayer metallic bonding and tive laser melting, directed energy deposition, and EBM. How-
thus improves the mechanical performance of DIW structures. ever, microstructure gradients and inter-dendritic element seg-
Therefore, saturation magnetization, magnetoresistance, elastic regation can occur from continuous thermal processing.[271] As
modulus, and hardness of the printed structures increased up such, adaptation of DIW for HEA production not only reduces
to a critical value of ≈47.6% of Ni content. energy requirements but also increases versatility and control
Infiltration of one metal into another has also been employed over the alloying composition. Kenel et al.[263] blended Co3O4,
as a technique to create fully dense, high-performance tungsten Cr2O3, Fe2O3, and NiO powders with a polymer binder (poly-
alloys. Tungsten (W) has the highest melting point of all ele- lactic-co-glycolic-acid), plasticizer (dibutyl phthalate), and sur-
ments and, as such, it is difficult to manufacture through tra- factant (ethylene glycol butyl ether) to print green body struc-
ditional melt-based techniques. Thus, researchers have begun tures followed by hydrogen reduction and sintering to develop
to explore if DIW can be used to overcome these challenges. CoCrFeNi alloy (Figure 10b). The resulting HEA structures
To create extrudable tungsten alloy slurries, tungsten oxide– were strong, ductile, dense, and compositionally homogeneous.
nickel oxide (WO3–NiO) powder was ball-milled to allow extru-
sion through finer nozzles (200 µm). The ball-milling approach
minimized agglomeration[261] along with reducing particle 4.6.3. Liquid Metal
sintering temperatures.[266] Minimization of the sintering tem-
perature for full densification of the printed alloy is only fea- Liquid metal (LM) comprises metals and metal alloys, which
sible for W when paired with a sintering agent such as Ni or melt at or near room temperatures, such as Mercury and Gal-
other group VIII elements.[261] The sintering temperature has lium. The AM community has invested more research efforts
also been found to influence the final grain size and porosity into Gallium due to the toxic nature of Mercury. However, Gal-
of tungsten and is a key factor to print more complex architec- lium has a melting point of ≈30 °C and cannot be printed at
tures requiring large features such as overhangs. Kenel et al.[261] room temperature. It requires the addition of other metals such
printed tungsten sheet-gyroids through H2 reduction sintering as indium, tin, or zinc, which reduces the melting point (≈15 °C
of WO3–0.6 wt%NiO with reduced mechanical anisotropy and for Indium), making it suitable for extrusion at ambient condi-
symmetric stiffness. Calvo et al.,[266] similarly, fabricated copper tions. These alloys of gallium are intrinsically stretchable and
infiltrated tungsten architectures by printing a polymer-based exhibit excellent electrical conductivity. Also, these alloys have a
ink containing WO3–0.5%NiO submicron powder, employed low melting point and fluidic behavior at or near room temper-
H2 reduction, and Ni-activated sintering before vacuum infil- ature that allows printing and patterning on various substrates,
tration. They found that infiltration of copper into tungsten including soft and biocompatible polymers and hydrogels.[6]
required small enough spacing to induce capillary forces As such, these alloys have gained substantial interest for appli-
(<500 µm) and achieve full densification. The resulting W-Cu cation in mechanically flexible[272,273] and soft electronics[265]
3D structures could be ideal for applications such as high emis- (Figure 10c-ii).
sion cathodes or ultrahigh-voltage electric contacts due to tung- Generally, bulk LM is a low viscosity (water-like) Newtonian
sten’s arc erosion resistance and the low thermal and electrical fluid and does not meet the rheological requirements for DIW.
resistance of copper. When exposed to air, a 1–5 nm thick passivating oxide layer
Due to its biocompatibility, chemical stability, high strength- forms spontaneously on the surface of the LM, which renders
to-weight ratio, and corrosion resistance, metallic alloys, e.g., non-Newtonian behavior to the fluid and allows the low vis-
titanium alloys, have potential applications in addressing bone cosity metal to readily flow within.[6] It is the oxide layer that
breaks and fractures. However, in vivo titanium has relatively provides stability and defines the geometry of the printed LM
low bioactivity and does not properly integrate with the sur- structures. Therefore, for continuous direct printing, besides
rounding bone. Moreover, manufactured titanium is often ensuring the common rheological requirements of the ink, pre-
anisotropic, which has been found to have significant effects cise control on the yielding (rupturing and reforming) of the
on bone-implant interface stress and strain,[270] ultimately oxide layer becomes a critical factor. Researchers have intel-
leading to bone deterioration. One approach to improve cur- ligently attempted to tackle the issue either by incorporating
rent titanium implants is to increase porosity.[181] Increasing additional mechanisms (mechanics) into the original printing
porosity not only assists with osseointegration but also reduces process or modifying the ink rheology using additives. One
approach is to bring the nozzle (which has an LM meniscus) a stretchable substrate, then stretching the substrate, freezing
in close proximity to a substrate to which the oxide adheres. the patterns in the extended state, and finally transferring it to
Then the motion of the nozzle, either horizontally or verti- an unstretched substrate.[278] This process can be repeated sev-
cally, allows sufficient stress to yield (or rupture) the oxide eral times to reduce a 120 µm feature down to 2 µm. The other
layer through mechanical forces of shear or tension. How- approach that gained attention is to pattern LM droplets.[274]
ever, since the physical contact between the ink and the sub- In this process, bulk LM or nanoparticles dispersed LM are
strate is critical in this technique, several factors must be taken loaded in a carrier solvent that can easily evaporate. Besides
into consideration during the motion of the nozzle (printing), these, several new tactics such as microcontact printing,[279]
such as printing speed, extrusion rate, adhesion, and distance freeze printing,[280] electrowetting assisted printing,[281] and
between the nozzle and the substrate, and topography of the laser-guided leveling assisted printing[282] have been applied to
substrate.[272] Following the motion of the nozzle, LM flows and advance the LM printing process and features of the printed
remains stable as the oxide layer rapidly reforms. Ladd et al.[274] constructs. Progress in LM printing is expected to open path-
showed that LMs can be drawn directly in the air via tension ways for its applicability in numerous applications, including
to form wires, which remained stable due to the formation of stretchable electronics (Table 3).
the oxide skin. However, the height of these wires and the pres-
sure applied during printing were critical to forming a struc-
ture without any collapse, bulge, or rupture. A variety of stable 4.7. Multimaterial DIW
structures in the form of cylinders, arches, bridges, and coils
were realized in this work and the smallest components fabri- One of the biggest challenges of conventional as well as many
cated were ≈10 µm. existing AM techniques is the simultaneous fabrication of more
Given the rapid increase in the device density and complexity than one material in a single geometry while maintaining its
of conductive pathways in electronic chips, the sub-millimeter structural stability and delivering functionality. In this aspect,
resolution achieved in the work of Ladd et al. is too large for the DIW has shown great promise as it enables the combination
electronic industry. Park et al.[264] demonstrated high-resolution of different materials and/or formulations into complex struc-
direct writing of LM, and the minimum width of the printed tures, thus reducing waste and production time by eliminating
line achieved was 1.9 µm. They used nozzles of varying diame- the need to assemble components. It also expands the design
ters to control the printing resolution. As shown in Figure 10c-i, space, enabling new products, composites, and devices with
the nozzle tip can be used to lift up the fine features of LMs structural and functional properties.
preprinted on substrates and then precisely relocated to another 3D structures with well-controlled composition and geometry
desired area to reconfigure their preprinted patterns into diverse can be designed and printed by multicore–shell DIW. By cre-
free-standing 3D structures. Thanks to the high stretchability ating multiple printable materials and tailored coaxial nozzles,
and the oxide skin of LMs, the preprinted features could be relo- Mueller et al.[285] printed architected lattices composed of mul-
cated while preserving the diameters of the printed filaments. ticore–shell struts. In this study, they investigated the fracture
The reconfigurable/lift-off LM DIW technique was used to mechanism in core–shell struts having a brittle epoxy shell and
make a reconfigurable antenna, reversibly movable 3D intercon- a flexible epoxy core with and without an elastomeric interface.
nections as mechanical switches, and a populated micro-LED They found that the presence of an elastomeric interface miti-
array with reconfigured 3D interconnects (Figure 10c-i). gates crack propagation from the shell to the core, thus exhib-
While the above-mentioned research works were focused iting both stiffness and toughness. Similar strategy was devised
on printing bare LM, the other approach for DIW of LM is to by Xia et al.[286] and Paredes et al.[287] to develop carbon fiber/
modify the rheological behavior of the LM using particle fillers ceramic and polymer/ceramic scaffolds, respectively, with
or other additives. However, this method does not require the core/shell struts. Xia et al. co-extruded the two inks containing
adherence of the LM ink to the substrate. Various additives carbon fiber and SiC (schematic of the printing process is
and fillers such as nickel particles[273,275] or platinum adsorbed shown in Figure 11a)). On the other hand, Paredes et al. devel-
carbon nanotubes[276] can be added to LM to form a thick paste, oped hollow ceramic scaffolds (rods) and then infiltrated with a
which facilitates printing layer by layer structure. Besides polymer melt by suction. However, in both cases, the outer shell
improving the ink rheology, additives can also help manipulate provided strength, while the inner core improved the toughness
the LM on a substrate. Ma et al.[277] reported a simple and ver- of the structure. Lorang et al.[288] demonstrated the patterning of
satile approach for direct patterning of LM using a magnetic hybrid organic-inorganic optical waveguides in straight, curved,
field after magnetic microparticles were dispersed into LM. A and out-of-plane configurations via DIW of photocurable liquid
moving magnetic field actuates the magnetic additive parti- core–viscoelastic fugitive shell inks. The printed waveguides
cles, thereby deforming the LM droplet into a continuous line. exhibit low optical loss throughout the visible spectrum.
Using this technique, they demonstrated LM patterning with The construction of multimaterial architectures generally
the minimum feature size of 500 µm on a variety of substrates, involves sequentially printing individual materials using mul-
including PDMS, hydrogel, paper, eggshell, glass vials, and tiple nozzles.[289–291] Printing one material at a time requires
hollow fiber tubes. meticulous alignment of each nozzle as well as the start-and-stop
Research in terms of understanding the mechanics of ink flow on demand. Besides, one must have precise control on
integrating LM to various substrates and improving feature the interface of the extruded lines to achieve a strong intercon-
resolution is still being pursued. For example, the resolu- nection. Using sequential multimaterial DIW, Blake et al.[289]
tion of printing can be improved by printing LM patterns on developed completely additively manufactured Li-ion batteries
Table 3. Summary of recent progress in DIW of metals and alloys.

Single component Titanium Printed origami structures from polyhedrons Tissue engineering scaffolds, biomedical Ahn et al.[23]
metals to cranes devices, or catalyst supports
Titanium Porosity-controlled scaffolds that mimic the Orthopedic applications, biomedical implants, Chen et al.[283]
mechanical performance of cancellous bone bone tissue engineering
Magnesium Well-controlled, structured pores from Biomedical implants and scaffolds Kleger et al.[255]
submillimeter to macroscopic scale by
salt-leaching
Copper Customizable hierarchical nanoscale pores Electrocatalysis, battery electrodes, fuel cells, Mooraj et al.[256]
(10–100 nm) by chemical dealloying supercapacitors, sensors, and actuators
Tin, iron, zirchonium, Complex architectures with 16 types of metals Batteries, heat exchangers, electrodes for Jakus et al.[257]
and more dye-sensitized solar cells, catalyst substrates,
and lightweight structures
Iron & nickel 5–50 µm hierarchical pores by space holder Light-weight construction, filtration, catalytically Kenel et al.[258]
leaching active materials, ion-exchange processes in
batteries, fuel cells, and thermal management
Tungsten Gyroid structures, double-wall gyroids, X-ray collimators, X-ray filters, composite Kenel et al.[261]
30 times higher energy absorption than lattice reinforcement, biomedical implants, and heat
structures exchangers.
Silver Laser-assisted DIW, 50-fold higher thermal Flexible electronics, photovoltaics, displays, Skylar-Scott et al.[262]
conductivity than as-printed, electrical resistivity sensors, and electrically small antennas
of 5.4 × 10−6 Ω cm, lower than bulk silver
Silver High bonding strength, 5.2% increase in resis- Batteries, sensors, lighting, displays, robotics, Zhou et al.[284]
tance after 1500 time bending test automation, and electronic skins for robotics
and prosthetics
Metal alloys Copper/steel Improved electrical conductivity by 400%, and Medical implants, sensors, and batteries Xu et al.[268]
the mechanical stiffness by 34%
Copper/nickel Nanocrystalline (<35 nm) solid with no apparent Cryogenics, functional devices Wang et al.[267]
porosity, DIW without any postprocessing
annealing
Tungsten/nickel Double-wall gyroids, reduced mechanical anisot- Reinforcement in composites, biomedical Kenel et al.[261]
ropy, and symmetric stiffness implants
Tungsten/copper Reduced the sintering temperature for full High emission cathodes, ultrahigh temperature Calvo et al.[266]
densification, finer nozzles (200 µm) heat exchangers, or biomedical implants with
high radiopacity
Titanium/aluminum Highly porous (up to 65 vol%), equiaxed grain, Supports for high efficient catalytic devices, Elsayed et al.[181]
carbide high compression strength microbial fuel cells, electrodes operating at
high temperature in aggressive chemical
environments, and mechanical damping
component parts
Titanium/boron/ carbon Compressive strength (1019–55 MPa), Bioimplants, aerospace, petrochemical, and Song et al.[269]
porosity (24–77%) automotive industries
Cobalt/chromium/iron/ High ductility and fracture toughness at Load bearing applications Kenel et al.[263]
nickel cryogenic temperatures, dense and composi-
tionally homogeneous structures
Liquid metals Gallium/indium DIW of eutectic Ga–In, a fluid with nonprintable Stretchable electronics, strain gauge devices, Boley et al.[272]
characteristics for inkjet technology conformable inductors, and capacitors
Gallium/indium/nickel DIW on printed paper, self-healing, easy to Flexible paper electronics Chang et al.[273]
repair circuits
Gallium/indium Soft sensor systems composed of 10 sensing Soft sensors, circuits, stretchable electronics Kim et al.[265]
units to measure finger joint angles
Gallium/indium Mechanically stable structures such as wires, Soft and stretchable electrical interconnects, Ladd et al.[274]
arrays of spheres, arches, and interconnects electrodes, antennas, meta-materials, and
optical materials
Table 3. Continued.

Gallium/indium High resolution with a minimum width of Reconfigurable antenna, reversibly movable Park et al.[264]
1.9 µm, successful lift-off of preprinted features interconnections, stretchable electronics,
wearable electronics, soft actuators, and
robotics
Gallium/indium/nickel High electrical conductivity (3.9 × 106 ± 9.5 × Stretchable and flexible electronics Daalkhaijav et al.[275]
105 S m−1) and stretchability (over 350% strain)
Gallium/indium/carbon Minimum diameters of about 5 µm, improved Soft and stretchable electronics Park et al.[276]
nanotube/ platinum mechanical strength and structural stability,
uniform and homogenous composites
Gallium/indium/nickel Direct patterning using magnetic field, the 3D structural electronics, antennas, touch sen- Ma et al.[277]
minimum attained feature size of 500 µm sors, and flexible displays
Gallium/indium 2 µm wide linear pattern, 60-fold reduction with Strain and tactile sensors Kim et al.[278]
respect to the initial dimension
(LIB). Combining the dry phase inversion technique and high to enable continuous printing of heterogeneous voxelated fila-
ceramic loading, they developed high-performance printable ments, which allowed for a powerful and rapid 3D printing pro-
Li-ion battery electrolytes. Then, using the same strategy, they cess. However, this work was limited to 3D objects with periodic
developed carbon/ceramic composite electrodes. Finally, they layouts since the nozzles were not independently switchable.
demonstrated sequential printing of the electrolyte ink over a Therefore, the development of MM3D printheads that would
composite electrode via DIW while maintaining expected func- ideally feature independently addressable nozzles with smaller
tionality in both layers. They achieved a tight and continuous diameters (for improving feature resolution) arranged in larger
interface, the desired trait for discharge voltage stability in arrays can be actively pursued. Xu et al.[268] developed a MM3D
a flexible energy storage device under mechanical load. The printing method to fabricate complex 3D steel structures with
sequential printing of multimaterial strategy was also used by removable supports. Leveraging the different melting tem-
Shen et al.[290] to print a microsupercapacitor (MSC). At first, peratures of the printing materials, a thermal treatment was
the anode and cathode were printed from two inks of vanadium designed to remove the polymer binder from the main ink
pentoxide (V2O5) and graphene–vanadium nitride quantum (Steel-PLA ink) and the secondary materials (Copper and alu-
dots (G-VNQDs), respectively, with highly concentrated GO dis- mina), which facilitated fabricating complex structures such as
persions. Finally, the gel-like electrolyte was printed between the enclosed hollows. Hansen et al.[295] created multinozzle arrays
electrode layers, which served as the separator for the MSC. The composed of hierarchically branching microvascular network(s)
3D printed MSC with interdigitated electrodes exhibited excel- and demonstrate high-throughput printing of single and mul-
lent structural integrity, a large areal mass loading of 3.1 mg cm, tiple materials over large areas (≈1 m2). Using this technique,
and a wide electrochemical potential window of 1.6 V. The various biomimetic architectures can be printed using func-
literature is strife with examples of sequential multimate- tional materials that could be utilized in various applications,
rial printing, most of which demonstrate the potential of this including self-healing polymer composites, lightweight foams,
technique for the realization of various electrochemical energy cellular constructs, and 3D scaffolds for tissue engineering.
storage devices[241,292] as well as sensors.[293] Wei et al.[292] dem- Modifications of the printing system as in mixing[296–298] or
onstrated a fully 3D printed and packaged LIB using DIW in switching[299,300] ink cartridges in situ during printing allow
which typical LIB manufacturing steps such as drying, electro- multiple materials to be printed continuously in a single pass
lyte infilling, calendaring, clamping, and heat-sealing processes through a single nozzle. Such modifications are often achieved
were eliminated by careful and intelligent ink formulation by incorporating a mixing device onto the printhead[296,297,299] or
(Figure 11c). Using biphasic semisolid carbon-ceramic mixtures using multiple ink reservoirs, each connected to the printhead
with enhanced conductivity as thick electrodes and polymers– by multiple capillaries,[300] or using both mixer and multiple
ceramic composites as separator and packaging, they produced reservoirs.[298] Thus, the nozzle can accept more than one ink,
a fully 3D printed LIB that exhibited excellent areal capacity. and the relative flow rate of each ink can be independently and
The tremendous potential of multimaterial DIW is also arbitrarily adjusted in time by means of a computer-controlled
reflected through the research works that involve printing a dispensing. This offers the advantage of attaining program-
whole structure with simultaneous dispensing of disparate inks mable control of local composition and property of the mate-
from an array of nozzles.[268,294,295] Skylar-Scott et al.[294] reported rial, thus realizing functionally graded materials. Ober et al.[296]
the design and fabrication of voxelated soft matter using multi- used an active mixer printhead to homogeneously mix two
material multinozzle 3D (MM3D) printing, in which the com- disparate inks and printed a silicone-based elastomeric ink in
position, function, and structure of the materials are tailored at which the concentration of a fluorescent pigment is continu-
the voxel scale (Figure 11b). They also demonstrated the seam- ously and discretely changed during printing (Figure 11d). They
less switching between multiple materials at high frequencies also resolved the kinetic constraints of printing chemically
Figure 11. Multimaterial DIW. a) DIW coextrusion methodology of a core–shell carbon fibers/silicon carbide (Cf/SiC) lightweight composite. Repro-
duced with permission.[286] Copyright 2019, Elsevier. b) Schematic of voxelated architectures printed using a single (0D) nozzle (top) and the 1D
(middle) and 2D (bottom) MM3D printheads (first column). Photographs of the corresponding 0D, 1D, and 2D four-material MM3D printheads
(second column). Photographs showing the top (top) and side (middle and bottom) views of a 4 × 4-nozzle, four-material, 2D MM3D printhead (third
column) Scale bars: 10 mm. Reproduced with permission.[294] Copyright 2019, Springer Nature. c) Fully 3D printed and packaged Li-ion battery (LIB)
made using multicartridge DIW. Reproduced with permission.[292] Copyright 2018, Wiley-VCH. d) Images of the cross-section of a 3D rectangular lattice
structure showing continuous change in fluorescent pigment concentration under bright light (top, left) and UV radiation (top, right). Mixing nozzle
in operation for 3D printing of a two-part epoxy honeycomb structure. A coin is shown to indicate scale (bottom). Reproduced with permission.[296]
Copyright 2019, National Academy of Sciences.
reactive materials. They printed a two-part epoxy, in which the patterns composed of multiple desired bioinks, at a speed an
resin and the curing agent were separately fed to the mixer order of magnitude faster than other nozzle based bioprinting
printhead, to generate the 3D honeycomb structure as shown modalities. They also produced complex and gradient con-
in Figure 11d. As a demonstration of tailoring the functionality, structs, which could find potential applications in tissue engi-
they varied the ratio of two streams of highly conductive silver neering and bioelectronics.
nanoparticle (bulk resistivity 5 × 10−4 ohm cm) and carbon col- Modification of multimaterial DIW may also include incor-
loidal inks (bulk resistivity 10 ohm cm) and thus continuously porating an external “control knob” into the printing process.
controlled the electrical resistivity of the printed structure. Liu For example, Kokkinis et al.[13] developed magnetically assisted
et al.[300] developed a rapid and continuous multimaterial extru- multimaterial DIW by incorporating add-ons such as the use
sion bioprinting technique, which is able to eject seven dif- of magnetic fields to manipulate particle orientation inside the
ferent types of bioinks individually and simultaneously using printed construct. An ink containing magnetically responsive
a tunable pneumatic single-print head system. Using this tech- anisotropic and stiff particles was printed to make a helicoidal
nique, they were able to construct topological planar and 3D staircase suspended in a UV light-sensitive liquid resin. 3D
Figure 12. Synopsis of materials used for DIW and their various applications.
printed layers of polymer-containing magnetized particles were 5.1. Electronic Components and Devices
exposed layer by layer to a magnetic field to orient all particles
in a layer. Defined exposure of the printed layer to UV light The flexibility, design freedom, and rapid development capa-
polymerizes and crosslinks the monomer phase of the ink, bility brought by DIW for micro/nano-scale material printing
eventually fixing the platelet orientation in the illuminated area. and/or structure development have found various applications
Thus, spatial control over the local composition of the printed in electronics. For example, well-controlled microstructure in
material was attained. Using the magnetically assisted mul- the DIW printed construct can offer exceptional electrochemical
timaterial DIW, they printed heterogeneous composites with performance by allowing better transfer of electrons and ions
excellent microstructural features and multifunctional shape- through the hierarchical porous structures.[251,301] These struc-
changing soft devices for mechanical fastening. tures are increasingly being employed for application in several
electronic components due to their high conductivity and high
specific surface area. These properties, specifically for energy
5. Applications of DIW storage devices, increase the contact area between the electrode
and electrolyte, thereby improving the device performance.
Given the rapid development thus far, DIW appears poised to The versatility of the DIW technique opens up possibilities for
deliver the next generation of designer materials for a wide novel design and facile fabrication of several energy storage
range of technological applications (Figure 12), including elec- devices such as batteries[79,289,291,292,302–304] (Figure 13a-i) and
tronics, energy storage, biomedical, structural, soft robotics, supercapacitors.[194,178,237,248,251,290,305,306] Environment-friendly
and food printing to name a few. The current advances in for- formulation of sandwiched[292] as well as interdigitated[291] full
mulation design and the fundamental understanding of the cell printing that includes efficient electrodes (Figure 13a-i)
rheological parameters that define “printability” will pave the of different materials and topology together with a range of
way for scaling up and industrial use of DIW for these specific electrolytes (solid and liquid) have been implemented. These
applications and beyond. devices have shown superior electrochemical rate performance,
Figure 13. DIW applications. a-i) Schematic illustration of direct-write assembly of interdigitated micro-battery architectures by printing LiFePO4 (LFP)
and Li4Ti5O12 (LTO) inks (top), SEM images of printed and annealed 16-layer interdigitated LTO-LFP electrode architectures (bottom left), and optical
image of 3D-IMA composed of LTO-LFP electrodes after packaging (bottom right). Reproduced with permission.[291] Copyright 2013, Wiley-VCH. (ii)
Schematic of the tactile sensor consisting of a base layer, top and bottom electrodes, an isolating layer, a sensor layer, and a supporting layer (top
left), top view of the tactile sensor (top right), and photograph showing the tactile sensor mounted directly above the radial artery (middle right) with
measurement signals of radial pulse under sedentary and postexercise states (bottom). Reproduced with permission.[293] Copyright 2017, Wiley-VCH.
specifically high areal capacitance, capacitance retention, high the potential of DIW for circuit design in various electronics
areal energy density, and power density, while displaying good such as solar cells, LEDs, transistors, and antennas[262,264,312,313]
stability. Furthermore, the DIW process shows the flexibility to (Figure 13a-iv). Besides these electrical components, the DIW
be used in conjunction with other technologies such as electro- technique has also been used to realize radiofrequency (RF)
deposition[248] or chemical vapor deposition[307] to deposit var- devices for the wireless network[314] and flexible nanogenera-
ious oxide nanoparticles on the printed structure and thereby tors[315,316] for electronic devices and 3D photonic crystals.[33,317]
obtain superior electrochemical performances.
DIW also enables the direct deposition of electronic mod-
ules, including the energy storage devices, onto various flexible 5.2. Biological and Biomedical Applications
substrates, implying excellent prospects for flexible electronic
production.[308] Printed structures/devices have shown mechan- DIW has shown enormous potential to be extensively applied
ical rigidity (no cracks upon bending) and flexibility along with in biomedical and tissue engineering applications due to its
excellent adhesion to the substrates while maintaining high versatile ability to print a wide array of materials in nearly any
electrical conductivity. DIW has provided new opportunities for arbitrary shape and dimension. These applications typically
the fabrication of wearable and flexible strain[272] and tactile sen- include artificial organ and bio-implants,[110,318] microvascular
sors[293] (Figure 13a-ii) with topological conformity, interwoven networks,[113] scaffolds for bone repairs/ substitutes,[217,218,283,319]
3D geometries, and programmable integration of multiple tissue regeneration,[217,320,321] (Figure 13e-ii,iii) and biomedical
materials and functionalities. It has greatly facilitated the devel- devices.[138,147] Printed scaffolds have been shown to provide
opment of strain sensors, thanks to its 1) ability to create micro the required mechanical response as well as biocompatibility
and nanoporous structures[309] (improves pressure sensitivity), and cellular integration. For example, DIW printed hydrogels
2) design freedom that facilitates increasing the nanofiller con- showed exceptional mechanical properties and excellent bio-
centration in the ink (decreases contact resistance and thus activity with eminent cell attachment on the surface of scaf-
improves sensitivity), and 3) versatility of materials that allows folds in physiological conditions (cell viabilities above 93%).[110]
utilizing conductive nanofillers (conductive network produces Besides, polymers, metals,[255,283,322] and ceramics[169,181,189,217]-
higher electrical resistance change, meaning improvement based bio-scaffolds have also been reported that have compa-
in the sensitivity). Lightweight, portable and wearable strain rable mechanical properties to human bones/cartilages[217]
sensors produced by DIW[301] can find application in human and excellent biocompatibility. It should be noted that bionic
motion detectors and human–machine interface sensors. pores are critical in medicine and bone implants as they can
Besides, DIW demonstrates the development of micro- guide tissue regeneration and osteointegration. DIW provides
electrodes[262,284] and electronic contacts/interconnects[279,310,311] a direct and facile control in terms of constructing porous bio-
using metallic/conductive nanoparticles as well as liquid metals implants and scaffolds for bone repairs/ substitutes and tissue
that can carry an electrical signal from one circuit element to regeneration.
another. Owing to its simple process, low cost, and digital pat- Compared to other manufacturing techniques, DIW can
terning ability, the technique can be an alternative to traditional deposit the designed number of cells,[323] or other bioactive[109]
lithographic processes for circuit fabrication. Planar or 3D and compounds onto the precise spatial position. The emerging
reconfigurable[264] complex interconnects (Figure 13a-iii) can be capability to direct-write a diverse palette of functional inks will
patterned on a wide variety of substrates, which demonstrate enable the mass democratization of patient-specific wearable
(iii) Optical image acquired during patterning of silver interconnects on a gallium arsenide–based 4-by-4 LED chip array. Reproduced with permis-
sion.[315] Copyright 2009, AAAS. and (iv) Optical image of an antenna during the printing process (left) and optical image of a completed antenna in
side and top (inset) views (right). Reproduced with permission.[313] Copyright 2011, Wiley-VCH. b-i) 90°/0° Flower morphologies generated by biomi-
metic 4D printing. Reproduced with permission.[11] Copyright 2016, Springer Nature. (ii) Comparison between printed hemitoroidal shell structures
comprising of opposing negative and positive Gaussian curvatures with an azimuthal print path at room temperature (left) and 200 °C temperature
(right). Reproduced with permission.[339] Copyright 2017, American Chemical Society. c-i) Optical image of the coaxial printhead connected to the core,
interface, and shell ink reservoirs (top left), schematic cross-sectional view of the core–shell (C–S) printhead, (top right), schematic illustrations of the
C–S and core–interface–shell (C–I–S) struts (cross-sectional and side views) (middle and bottom). Reproduced with permission.[285] Copyright 2018,
Wiley-VCH. (ii) Schematic illustration of the progressive alignment of high aspect ratio fillers within the nozzle during composite ink deposition (top),
triangular honeycomb structures composed of SiC-filled epoxy (bottom). Reproduced with permission.[100] Copyright 2014, Wiley-VCH. d) Chocolate
with plant sterol powder and different infill patterns (top left). Reproduced with permission.[357] Copyright 2019, Elsevier. cookie dough (with xanthan
gum) before and after baking (bottom left), Reproduced with permission.[358] Copyright 2019, Elsevier. vitamin-D enriched orange concentrate with
wheat starch and k-carrageenan (top right), Reproduced with permission.[359] Copyright 2018, Springer Nature. printed lemon juice gel in ring shape
(middle right), Reproduced with permission.[158] Copyright 2018, Elsevier. and meat (bottom right) Reproduced under the terms of Creative Commons
Attribution license.[355] Copyright 2017, IOP Publishing. e-i) Scanning a doll face and depositing of a 4.5 wt % Flink containing A. xylinum onto the
face using a custom-built 3D printer. Reproduced under the terms of Creative Commons Attribution license.[26] Copyright 2017, AAAS. (ii) Schematic
images of cardiac muscles and a simplified muscle structure fabricated by 3D printing (top), optical and SEM images showing the uniaxially aligned
microfibers in the longitudinal direction of surface and in the cross-section of the polycaprolactone (PCL) microfibrous (PAPS37C) mesh structure,
showcasing of the well-aligned C2C12 cells along the microfibril direction by diamidino-2-phenylindole (DAPI) (blue)/phalloidin (red) images of surface
and cross-section after 7 d of cell culture, and immunofluorescence staining of myosin heavy chain (MHC) (blue = nuclei; green = MHC) after 14 d of
cell culture (bottom). Reproduced with permission.[320] Copyright 2018, Wiley-VCH. (iii) 3D microvascular networks with exposed microvascular chan-
nels (top) and fluorescent image of the microvascular network (bottom), fabricated via omnidirectional printing of a fugitive ink (dyed red), scale bar:
10 mm. Reproduced with permission.[113] Copyright 2011, Wiley-VCH.
devices and smart biomedical implants for applications such new dimension to engineering design and optimization for
as health monitoring and regenerative biomedicines. Fur- structural applications.[211,221]
thermore, the printing dynamics have proved to maintain cell The reinforcements/fillers in DIW printed parts have
stability, and the room temperature extrusion facilitates soft been widely reported to enhance the mechanical properties
matters such as biopolymers,[324,325] cells,[323] and bacteria[26] and introduce new functionalities.[332] Many of these studies
(Figure 13e-i) to survive the printing process. These may serve involved high filler loading to develop a filler-dominant struc-
as ideal organ building blocks for biomanufacturing patient- ture with high mechanical strength.[333] Moreover, the shear
and organ-specific tissues with the desired cellular density, forces arising during extrusion through the micronozzle align
composition, microarchitecture, and functionalities. fillers (fibers/2D materials/CNCs) in the matrix during printing
The 4D dynamically reconfigurable constructs with tunable that gives a close control over filler orientation within the
functionality and responsiveness opened possibilities of cre- printed parts.[100] This makes DIW an efficient manufacturing
ating shape-morphing and/or self-healing[326] architectures for technique to develop composite materials for automotive, aero-
tissue engineering and regenerative medicine applications. The space, space, and civil engineering applications. By integrating
time-evolving behavior of 4D printed thermoplastic,[138] ther- external field control and mechanical movement into the
moset,[326] hydrogels,[137] and liquid crystalline elastomers[327] existing process, one can have an even higher degree of con-
showed the possibility of various biomedical devices including trol on the spatial distribution of the reinforcement[84,85,334,335]
vascular stents,[138] implantable electronics/biosensors,[109] inside the matrix (Figure 13c (ii)). Such flexibility coupled with
scaffolds for vascular and broken “blood vessel” repair[139] and advanced features such as multimaterial and/or multinozzle
drug delivery.[328] Freedom of material along with multimate- printing opens up new possibilities to create functionally
rial printability facilitates such a wide range of applicability graded materials[297,336] and damage-tolerant structures[85,285]
of the DIW technique in the field of biology and biomedical (Figure 13c-i).[211]
engineering.[132,329]
5.4. Soft Robotics and Actuators

5.3. Structural Applications
DIW of polymeric materials has found a wide variety of
DIW has evolved as a facile, robust, and green manufacturing applications in soft robotics, biomedical devices, and actua-
method with the ability to introduce new structures using tors.[131,337] The integrated design and rapid fabrication
complex architecture,[34,57,224] hierarchical porosity,[169,249,24] and approach enabled by DIW offers the assembly of several poly-
functional networks of cellular materials.[25,100] Such archi- meric materials, including hydrogels,[337,338] liquid crystalline
tected structures have been shown to possess better mechanical elastomeric (LCE),[128,131,327,339] shape memory polymers,[138]
properties suitable for a myriad of structural and engineering elastomers,[139,318,340] and polymer composites[341] into com-
applications. To date, several architected lattices, including hon- plex shapes with a programmed mechanical response. Typi-
eycombs,[100] woodpiles with solid,[9,34] and foam struts,[24,25] cally, 4D printing[132] facilitates the realization of such devices.
have been fabricated with high specific stiffness and strength. Using a suitable external stimulus, such as, light,[130] magnet,[13]
Also, by designing and printing complex and highly ordered heating,[128] it is possible to induce specific mechanical as well
architectures in cellular solids, it is possible to create mechan- as biological[137,318] motions/deformations into the structure,
ical metamaterials to obtain unusual mechanical responses.[34] as presented in Figure 13b-i,ii.[11,339] DIW approach has been
Thus, the ability to decouple properties via architectural control used to fabricate self-folding microstructures,[11] smart grip-
allows unique performance in the structures such as ultralight- pers,[342,343] actuators,[131,327,344] hydraulic valves,[345] and robotic
weight,[100] high-stiffness,[25] and high-strength materials,[60] hands. Structures showing controlled physical movements
tunable Poisson’s ratio,[57] and negative stiffness.[34] and those with stress blocking as well as good work capacity
Various strategic fields such as transportation, buildings, can be fabricated by DIW.[132] These structures can lift a load
sports goods, military, aerospace, and space applications significantly heavier than their own weight.[327,339] Thus, DIW
demand efficient lightweight structures. This, in turn, requires offers the possibility of controlling the locomotion and work of
a combination of strength and toughness at low density; how- printed soft devices at desired locations with desired shapes,
ever, these mechanical properties are typically mutually exclu- thus offering smart actuation.[346] The printed soft robots and
sive. DIW opens new avenues to produce a wide range of actuators are expected to augment hard robots, supplement
nature-inspired composite systems having respective hard and extend them, and provide new capabilities that they cannot
and soft phases and controlled architecture at multiple length match such as, safety, simplicity, low cost, and lightweight.[347]
scales. For example, printed ceramic scaffolds with controlled
porosity have been infiltrated with liquid metals[330] and liquid
polymers[331] to create interpenetrating phase composites. By 5.5. Food Applications
creating multiple printable materials and tailored coaxial noz-
zles, it is also possible to generate architected lattices composed Food printing, especially in areas such as military, space,
of multicore–shell struts that simultaneously possess high stiff- and medicine, has found promising potential to address the
ness and toughness.[285,286] DIW’s unique capability to integrate growing need for personalized nutrition, design customization,
complexity, composition, stiffness, and toughness results in supply chain simplification, and optimization of material use/
highly-optimized bioinspired 3D structures that add an entirely costs. 3D printing of food can open a new frontier considering
special environments or situations in which processing and/or Another drawback of DIW is its static cost of production,
finding materials can be challenging, restrictive, or expensive, similar to any other AM technology, which means the cost
such as for space food applications or for catering to the needs of a single unit remains the same even when the production
of dysphagia patients.[152,348] A myriad of food materials has process is scaled up. Thus, DIW manufacturing is only cost-
been successfully printed—from easily-extrudable materials competitive if the production volume is small as it requires a
such as chocolate,[349] cheese,[156] edible hydrogels,[350] cookie less initial investment. In contrast, traditional manufacturing
dough,[351] and dairy[352] to challenging-to-process food mate- processes have a higher initial cost than that of DIW, although
rials including fruits,[353] vegetables[354] and meat, as shown in it is often compensated when the production volume is ramped
Figure 13d.[355] Furthermore, modifying the print setup with up.[361] DIW, on the other hand, cannot avail such benefits of
additional features such as in situ cooking or gelation[356] can the economies of scale. Although this constraint exists in all
broaden the scope of food printing. Although the advent of additive manufacturing processes, DIW, despite needing the
DIW in food printing is still in its infancy, leveraging the ability least initial investment, is unable to overcome it. Such an issue
of customization and versatility will allow for customized food with upscaling is one of the most significant impediments to
items and new levels of artistry and control, leaving landmarks DIW’s adoption for mass manufacturing.
in food science and technology. One of the limitations of layer-by-layer deposition of DIW
is the inverse relationship between print speed and interface
integrity. High-speed printing results in poor interface fab-
6. Current Challenges and Limitations rication, whereas a better interfacial structure calls for lower
printing speeds.[132] This mutual exclusiveness is a great limita-
Despite overall versatility and freeform printing capabili- tion for the present DIW technology and is especially observed
ties, DIW is yet to be widely adopted at the large-scale indus- for large-scale printing of the structures. Furthermore, the inter-
trial manufacturing level and is mostly limited to rapid face may suffer from structural defects such as trapped gas,
prototyping.[10] The major challenges and limitations that are voids, or irregularities, resulting in poor interlayer bonding.
hindering its widespread commercialization can be listed as A number of postprinting ways have been proposed to solve
follows. this problem, such as hot or cold isostatic pressing or lami-
Printing resolution and speed of DIW are still lagging the nation. However, these post-printing treatments are energy-
desired optimal levels for the technology to be mass democ- demanding. Thus, removal of the structural defects from the
ratized and used in industrial sectors. With its current capa- interlayer spaces using high-resolution printing techniques
bilities, fabricating large-scale structures with intricate design with minimal or no post-printing treatments is a new challenge
and fine architectural details would require impractical time for researchers in the case of 3D structure development.
scales and efforts for ink formulation and parameter optimi- Another limitation of DIW is the sole confinement of the
zation.[10] This is a great barrier to the commercialization of director patterns in the x-y plane. A greater degree of flexibility
DIW technology. Moreover, not all of the printed structures can be realized in serving the strategic fields by developing
possess material properties superior to their existing state- an omnidirectional director pattern. Despite a few reports of
of-art 3D printed or traditionally manufactured counterparts. omnidirectional printing,[113,315,362] vertical building remains a
For instance, DIW printed lithium batteries exhibit less challenge for the present DIW technology because of the struc-
energy and power density compared to nonprinted lithium tural deformation[363] or failure caused by the structures’ self-
batteries.[301] Similarly, printed flexible piezoelectric nano- weight. This is a problem that gets intensified as we try to move
generators display less energy output than non-printed ones. towards larger production due to the sagging of the large over-
Thus, future advancements of DIW require large-scale pro- hangs and long beams in bulk structures.[10] Overcoming this
duction capabilities with improved efficiency to replace cur- challenge beyond ink optimization might open up a wide array
rent standard devices and structures. of large-scale structural applications that are yet to be realized
Although the energy demand of DIW is significantly lower via DIW.
than most traditional manufacturing technologies, the printed During fiber-reinforced composite fabrication, DIW is often
structures often require postprinting processing that could subjected to nozzle clogging as the individual length of the rein-
increase the overall production cost and time. Therefore, forcing fibers is comparable to the dimensions of the nozzle
while developing an environment-friendly and sustainable diameter. Thus, only a few misaligned fibers are enough to
manufacturing technique, the cost of the energy-demanding clog the nozzle. Even for low volume fractions, nozzle clogging
consolidation treatments such as drying or sintering should may result from dendrite-like agglomeration of particles in the
be considered. DIW practitioners address this issue by either nozzle wall.[364,365] In addition to that, long fibers can interact
minimizing the post-printing procedures through the integra- with more particles that facilitate fiber entanglement.[89] Thus,
tion of consolidation and shaping in a single step or using a big challenge for DIW technology is to minimize the nozzle
more efficient sintering technologies (e.g., cold or field-assisted clogging with appropriate pre-printing processing.
sintering).[10] Despite these possible solutions, some of these Print parameters such as nozzle diameter and nozzle flow
sintering technologies are only applicable to certain categories path limit the resolution of the printed fibers and the printed
of materials. For instance, field-assisted sintering is only appli- pattern.[366] While DIW has been extensively used to fabricate
cable for structures containing magnetic particles.[360] Thus, complex architectures in the microscale, it is yet to be utilized
minimizing post-printing procedures and sintering technolo- for the fabrication of nanoscale architecture. Such limitation
gies can be challenging. greatly hampers the versatility of DIW and narrows down
its field of application. Furthermore, different materials are art developments and findings in the field have been reviewed
extruded under different conditions, and no general guideline while elucidating the technique’s capability to fabricate intricate
has yet been developed that correlates the material specifica- 3D structures whose functional response relies not only on the
tions with the optimizing conditions. Thus, the present DIW material’s microstructure but also on the architecture and topo-
technology lacks extensive research in this strategic field of logical features. The various ink formulations used to prepare
application. engineered structures with desired functionalities have also
DIW imposes a definite criterion of appropriate rheological been discussed. We also explored the myriad of applications
characteristics of the printing material. Only those materials enabled by DIW, ranging from flexible electronics, structural
that can be transformed into a paste or ink while satisfying the applications to food and tissue engineering as well as other bio-
criteria for continuous extrusion can be a part of the DIW mate- medical implementations. Finally, with the current challenges
rial library. Thus, formulating inks for newly developed or dis- and limitations of DIW highlighted in the earlier section, the
covered materials can be a challenging task. Here, a noteworthy future prospects of DIW will be discussed to shed light on pos-
challenge for ink preparation is that there are no analytical sible opportunities to push the boundaries of scientific research
models that can correlate the ink rheological properties with and development in this regime.
the product performance. Thus, optimization of the ink formu-
lation or modification of the printing setup based on the newer • Advances in DIW have demonstrated the realization of many
materials is also an important criterion to fulfill. For instance, natural structures for structural and functional applications.
incorporating a reconfigurable printing nozzle that can modify To facilitate future research works, a large data library of 3D
itself in shape and functionalities based on the demand.[367–369] models of different natural structures with their organized
This kind of nozzles allow a dynamic regulation of the mechan- spatial coordinate configurations can be prepared. Such a
ical and physical behaviors by altering spatial contour through library can be synchronized with an Artificial Intelligence
shape transformation. Such a reconfiguration process can be (AI)-based autonomous DIW system that will choose a suit-
associated with topology-based printing parameter optimization able material model for printing specific objects for specific
methods. applications. Furthermore, machine learning-based analysis
For multimaterial printing, it is necessary to switch between may establish a correlation between the microscopic textures
materials very rapidly.[10] This requires rapid changes in of the interconnected porous network with the macroscopic
printing variables (e.g., pressures and flows) to be compatible properties. It can further be facilitated with other advanced
with the atmospheric fluctuations. This may call for a more algorithms such as support vector machines and Bayesian
stringent condition on the printing variables during multimate- modeling to predict the structural information (e.g., load-
rial printing. Although multimaterial printability has been an bearing capacity, controlled porosity, impact resistance,
intriguing feature of DIW, it has not been possible to develop strength, toughness, high-temperature durability, etc.) of
structures with materials having significantly different or con- different composites from microstructural inputs (e.g., ar-
trasting properties such as thermal stability. Owing to the dif- chitectural design, porosity, layer by layer deposition, rein-
ferent post-printing drying or sintering conditions, for instance, forcement dispersion, degree of adhesion with the composite
it has not been possible to achieve multimaterial printing of 3D matrix, different alignment configuration, etc.). At a certain
structures containing alternate layers of metal/ceramic (hard- degree of sophistication, such prediction may even be possi-
ordered phase) and polymer (soft-disordered phase). ble by solely analyzing the architectural networks of constitu-
In the case of bioprinting, although DIW technology has ent materials of the composites before the printing.
laid the foundation for cell patterning for scaled-up organ and • Multiscale correlational models can have far-reaching pros-
tissue fabrication technologies,[370] it has various limitations, pects and implications in AM especially in biomimetics.
including mechanical properties, printability, shear-stress- Under evolutionary pressure, nature has developed certain
induced cell deformation, tissue biomimicry, biocompatibility, characteristic architectures based on the specific surround-
poor resolution, degradation kinetics, and limited selection of ing environment. On the other hand, engineering applica-
the materials due to the need for a quick encapsulation of the tions may not always be analogous to the same environment.
cells via gelation.[371] Excessive or uncontrolled friction gener- Therefore, a bioinspired structure, which is most suited for
ated in the nozzle tip wall during extrusion reduces the viability that particular environment, may not demonstrate similar
of cells when the bio-ink concentration or cell density is high. performance in other environments. For example, a printed
Therefore, one needs to put additional effort in ensuring the structure mimicking the seashell morphology (mixed hard-
printing environment and parameters that are conducive to soft soft phase) developed by evolutionary means may provide
sensitive biomaterials (cells, tissues, bacteria, etc.). excellent performance in an ambient environment but can
fail drastically in moderate to high-temperature applications.
Thus, a potential solution to serve such strategic fields can be
7. Summary and Future Prospects combining multiple and multiscale architectural intricacies
of different natural materials into a single printed substance,
In this review, a thorough assessment of the DIW technique in based on the correlational model.
printing a wide range of materials with intriguing properties • One key challenge of the DIW system is to develop printable
and functionalities has been presented. We have delineated the ink having a proper rheological response. Different viscos-
DIW extrusion process along with a discussion on the suitable ity models have been developed in this regard to represent
rheological characteristics of the ink for DIW. The state-of-the- the non-linear relationship between shear stress and viscosity
that are widely being used to tune the ink rheology for con- of each layer (sometimes referred to as z-axis resolution) is
tinuous printing. However, ink rheology can be affected by a often the simplest parameter to mitigate the step effect. Typi-
number of parameters other than the shear stress. Examples cally, when a part is printed with a smaller layer height, it will
of these parameters are reinforcement/additive concentra- reduce the layer-by-layer effect, thus producing a smoother
tion, orientation/degree of loading, length scale, printing surface. Although this will lead to higher accuracy, print time
temperature, etc. No such model has been established yet to will be increased. Therefore, to overcome the step effect,
correlate the ink rheology with these modifying parameters. the most obvious research direction is to surpass the cur-
As of now, the present viscosity tuning method is completely rent state-of-the-art z-axis resolution of DIW. Furthermore,
based on trial and error of different additives, thermodynamic to improve interlayer bonding and subside the step effect,
coordinates, nozzle geometry, etc. However, in recent years, the layers can be “in situ welded” with the help of localized
physics-informed neural networks have shown great poten- electromagnetic wave-assisted heating at the interfaces. The
tial in function approximation and have been able to develop localized heating process should adjoin two printed filaments
relationships between viscosity and loading wt%.[372,373] Thus, by melting their interface, resulting in an increase of the in-
developing a deep neural network or an analytical model that terlayer bond strength without compromising the dimen-
can anticipate the rheological properties of the ink from its sional accuracy of the part. Furthermore, since the step effect
constituents and other process parameters will accelerate the originates at the interface of two cylindrical filaments, Finally,
ink preparation and further extend the library of printable the layer-by-layer problem can also be solved by optimizing
materials. the nozzle geometry, print parameters, and ink rheology to
• Numerical modeling and simulation of the printing process ensure that the ink extrudes with a near-rectangular cross-
may provide great insights into the physics of printing. Par- section rather than the cylindrical filamentary shape. This
ticularly, simulating the flow behavior of micro and nano- will increase the inter-filamentary contact area, thus enhanc-
particles inside the moving matrix and their interaction can ing z-axis mechanical characteristics.
be used to predict the flow physics at various length scales.
Thus, a molecular approach can be best suited to serve this In summary, with such promising prospects in the near
purpose where each molecule is simulated individually future and beyond, DIW, with its’ unique ability to print a wide
within the computational domain. However, such computa- variety of materials with novel characteristics and applications,
tions are very time-consuming and costly. Thus, a mesoscale can be the next cutting-edge manufacturing technique.
approach, for instance, the direct simulation Monte Carlo
(DSMC) method, could be more suitable to simulate such
ink flow. Acknowledgements
• Continuum plasticity-based damage model can be used in
the finite-element-method (FEM) simulation environment to M.A.S.R.S., A.M., N.P., and M.S.H.T. contributed equally to this work.
quantitatively investigate the macroscopic physical properties The authors gratefully acknowledge the support of Ali Zein Khater for
discussion on the ink rheology section and for his help in preparing
of the printed structures. Considering a suitable model, tran- Figure panel (a).
sient analysis can be performed to investigate different as-
Note: The text relating to “dye-sensitized solar cells” in Table 3 was
pects of dynamic loading such as stress concentration, crack corrected on July 14, 2022, after initial publication online.
propagation, heat dissipation path mapping during external
loading, etc. Such analysis can be of great importance in se-
lecting and optimizing the physical process parameters to
improve the performance of the printed structure and manu- Conflict of Interest
facturing efficiency. The authors declare no conflict of interest.
• Finite element simulations can be further coupled with deep
learning methods to optimize the composition and geometric
design of composite materials. Based on the machine learn- Keywords
ing predictions, topology optimized multimaterial structures
can be manufactured using DIW that have desired mate- 3D printing, ceramics, direct ink writing, metals, polymers
rial properties and their combinations. Through intelligent
Received: November 3, 2021
transformation or modification of the print setup, tuning the Revised: February 23, 2022
ink formulation and/or pursuing a sophisticated engineer- Published online: April 28, 2022
ing approach, multimaterial printing of drastically different
materials (metals/polymers or ceramics/polymers) should be
investigated. This can lead to the concurrent attainment of
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M.A.S.R. Saadi completed his B.S. in Materials and Metallurgical Engineering from Bangladesh
University of Engineering and Technology (BUET), during which he studied the effect of multi-
scale reinforcement particle size on mechanical and thermal properties of polymer composites.
During his M.S. in Mechanical and Aerospace Engineering at the George Washington University,
his work focused on nanomechanics and electronic structure of organic photovoltaics and 2D
materials. He is currently pursuing a Ph.D. degree in Materials Science and NanoEngineering
at Rice University, where he is working on the development of high-performance and sustain-
able bionanocomposites, and fabrication of multifunctional materials via additive manufacturing
technologies.
Alianna Maguire is a Bioelectronics NSF Research Traineeship Fellow and a Ph.D. student in
the Department of Materials Science and Nanoengineering at Rice University. She received her
Bachelor’s in Materials Science and Engineering from Rensselaer Polytechnic Institute. During her
undergraduate studies, Alianna researched the effect of nanofiber diameter on neural growth and
elongation. She also worked to improve the thermal capacity of Nafion-based proton exchange
membrane fuel cells through nanocomposite development. Alianna currently works in the Ajayan
group and Lou group on the development of novel nanocomposites and harnessing additive
manufacturing techniques to improve mechanical performance of materials across scales.
Neethu T. Pottackal is a Rice Innovation Ph.D. fellow in the Department of Materials Science and
Nanoengineering at Rice University. She received her B.S. in Materials Science and Engineering
from Cornell University in 2020. Previously, as a Rawlings Cornell Presidential Research Scholar
at Cornell’s Food Science and Technology Department, she worked at the intersection of mate-
rials science and food science, particularly valorization of food waste for water purification and
food preservation. At the Ajayan Research Group, Neethu currently works on finding innovative
solutions to food sustainability issues, such as novel coatings for extension of shelf-life and 3D
printing of biomaterials/food.
Md Shajedul Hoque Thakur received his B.Sc. in Mechanical Engineering from Bangladesh
University of Engineering and Technology (BUET) in 2021, where he worked on the mechanical
and vibrational characteristics of functionally graded nanomaterials. He also worked on the
extraction of material properties through multifidelity deep learning from molecular dynamics
simulation. At present, he is a graduate student pursuing Ph.D. in Materials Science and
NanoEngineering at Rice University, working in the Ajayan 3D Printing group. His current
research interest is to integrate multiscale modeling and structure-property relationships with
additive manufacturing for the design and fabrication of metamaterials and composites.
Maruf Md. Ikram received his B.Sc. in Mechanical Engineering from Bangladesh University of
Engineering and Technology (BUET) in 2021, where he worked on the flow behavior analysis
at both macro and microscale. He also worked on the computational cost optimization of the
microscale flow simulation through multifidelity deep learning from molecular dynamics simula-
tion. At present, he is working as a lecturer at Ahsanullah University of Science and Technology,
Bangladesh. His current research interest is to merge machine learning with conventional additive
manufacturing for the design and fabrication of composites and metamaterials.
A. John Hart is professor of Mechanical Engineering at MIT. He is also director of the MIT
Laboratory for Manufacturing and Productivity and the MIT Center for Additive and Digital
Advanced Production Technologies (APT). John’s research and teaching activities at MIT focus on
the science and technology of production, including additive processes, automation, advanced
materials, and data science. John holds a BSE from the University of Michigan, and SM and Ph.D.
from MIT. He is also a co-founder of startup companies Desktop Metal and VulcanForms, and a
Board Member of Carpenter Technology Corporation.
Pulickel M. Ajayan earned his B.Tech. in metallurgical engineering from Banaras Hindu University
and Ph.D. in materials science and engineering from Northwestern University. In 1997, he joined
the materials science and engineering department at Rensselaer Polytechnic Institute (RPI) as an
assistant professor and was the Henri Burlage chair professor in Engineering until he left RPI in
2007. Currently, he is the Benjamin M. and Mary Greenwood Anderson Professor in Engineering
and the founding chair of Department of Materials Science and NanoEngineering at Rice
University. Professor Ajayan’s research interests include synthesis and structure-property relations
of nanostructures and nanocomposites, and their applications.
Muhammad M. Rahman is an assistant research professor at Rice University. He received his

Ph.D. from Cornell University, where he studied the structure–property relationship in green nano-
composites. His primary academic interest lies in interdisciplinary materials science research,
using an engineering and biology perspective to fabricate nature-inspired hierarchical composites
for various applications. He is designing next-generation composites via advanced manufacturing
technologies, with an emphasis on sustainability for load-bearing structures, foods, textiles,
energy, and environmental applications. Additionally, he is interested in exploring the hierarchical
architectures and geometry’s effect in designing new composites with distinctive multifunctional
properties.

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Direct Ink Writing: A 3D Printing Technology for Diverse

Manufacturing (AM) is the latest of these

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Muhammad M. Rahman is an assistant research professor at Rice University. He received his

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