Additive Manufacturing 47 (2021) 102322

Contents lists available at ScienceDirect

Additive Manufacturing
journal homepage: www.elsevier.com/locate/addma

Research Paper

Multiphase direct ink writing (MDIW) for multilayered polymer/

nanoparticle composites
Dharneedar Ravichandran a, Weiheng Xu a, Mounika Kakarla b, Sayli Jambhulkar a,
Yuxiang Zhu a, Kenan Song c, *
a
Systems Engineering, The Polytechnic School (TPS), Ira A. Fulton Schools of Engineering, Arizona State University, Mesa, AZ 85212, USA
b
Materials Science and Engineering, The School of Engineering of Matter, Transport and Energy (SEMTE), Ira A. Fulton Schools of Engineering, Arizona State University,
Tempe, AZ 85281, USA
c
The Polytechnic School (TPS), The School of Engineering of Matter, Transport and Energy (SEMTE), Ira A. Fulton Schools of Engineering, Arizona State University,
Mesa, AZ 85212, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Additive manufacturing has advantages in freedom of design, rapid prototyping, and waste minimization.
Additive manufacturing However, one bottleneck in 3D printing polymer/nanoparticle composites has been the lack of high-precision
Direct ink writing structural control, especially without sacrificing manufacturing rates. For the first time, this study demon­
Composites
strated the design and development of a new additive manufacturing mechanism, the Multiphase Direct Ink
Microstructures
Mechanics
Writing (MDIW). By matching the viscosity between polymer solutions/nanoparticle suspensions, an individual
line composed of a desirable number of sublayers (i.e., 4, 8, 16, 32, 64, 256, 512) was printed. A thin-ply
structure with continuous ink deposition showed a strong dependence upon these layer numbers per printing
line or the unit layer thickness. The 64-layered structure showed the highest modulus, strength, and energy
absorption at a specific strain of 30% (E30% strain) (i.e., 5 times increase in Young’s modulus, 3 times growth in
ultimate tensile strength, and 3.5 times improvement in E30% strain compared to the PVA). The enhancement in
composite mechanics was due to thin layer thickness that improved the interfacial interactions and nanoparticle
distribution homogeneity. The interfacial interactions between layers also facilitated the nanotube alignment and
affected the crystallization behaviors. Our MDIW method is compatible with natural-, synthetic- and biopolymers
as long as the feedstock rheology is well-managed, showing broad applications in structural systems, thermal
insulation, electrical conductivity, optical reflectance, and biomedical scaffolds.

1. Introduction most of these 3D printing methods find it challenging to use multiple

Additive manufacturing, commonly known as 3D printing, is a
manufacturing technique that builds layer-by-layer materials. 3D
printing has advantages over traditional manufacturing in rapid proto­
typing, complicated design, and material sustainability [1,2]. The
application of 3D printing in customizing personal protective equipment
(i.e., N95 masks, ventilators, nebulizers) during the recent COVID19
breakout also showed its enormous potential in decentralized
manufacturing and independence of international supply chains [3].
The main-stream 3D printing mechanisms include vat-polymerization
(e.g., stereolithography (SLA)), material jetting (e.g., direct inkjet),
material extrusion (e.g., fused deposition modeling (FDM)), and
powder-based-fusion (e.g., selective laser sintering (SLS)) [4]. However,
materials and simultaneously control their deposition orders. A simple
material mixture in monomer resins, dilute solutions, extruded fila­
ments, or blended powders requires uniform phase distribution and
significantly limits the mixing recipes for specific applications [5,6].
Direct ink writing (DIW) is a variable of FDM, where the latter uses
solid polymer filaments while DIW is compatible with a broad range of
inks in the form of polymer solutions, hydrogels, and aerogels [7]. DIW
is different from material-jetting-based polyjet or multijet and relies on
extruding highly viscous, shear-thinning solutions or gels [8,9]. Subse­
quent solvent exchange [10], liquid evaporation [11],
temperature-induced phase change [12], and UV/laser-assisted cross-­
linking [13–15] can facilitate the solidification procedures. One weak­
ness of polymer-involved DIW at the presence of solvent is fragile and

* Corresponding author.
E-mail address: Kenan.song@asu.edu (K. Song).

https://doi.org/10.1016/j.addma.2021.102322
Received 19 January 2021; Received in revised form 25 August 2021; Accepted 11 September 2021
Available online 16 September 2021
2214-8604/© 2021 Elsevier B.V. All rights reserved.
D. Ravichandran et al.
weak structures, limiting its primary applications to biomedical scaf­
folds or soft robotics that do not require high stiffness [16–18]. Com­
posite engineering is an efficient strategy for improving soft matter
mechanics, generally involving reinforcement fillers of nanoparticles.
Some reported protocols have focused on mixing strategies (e.g., ball
milling) and particle surface treatment for high polymer/particle in­
teractions. However, selective nanomaterial deposition in 3D printing
for enhanced mechanics has drawn little attention [8,19].
Layered structures have significant applications in thin-ply laminates
[20], thermal insulation or fire retardance [21], microelectronics [22],
optical reflectance [23], biomedical scaffolds [24], and gas-barriers in
packaging [25]. For example, manual stacking of thin-ply composites
can produce a layer thickness above 200 µm for high damage tolerance.
Coextrusion enables layered flame-resistant electrolytes for batteries
[26], high strength and stretchable packaging [27], and high refractive
index multilayered films as distributed feedback laser [28]. Further
improvement of the manufacturing precision of fine features and their
structural complexity (e.g., 3D, hierarchical, functionally graded) will
enable new functions and applications. For example, the reduction of
layer size (e.g., thickness within the plane or along the plane normal
direction) can allow thin-walled structural being folded/rolled under
strains for high packing efficiencies, pressurized structures of tanks [29,
30], or greater freedom in designing lightweight solar arrays and an­
tennas for outer space applications [31]. Thus, 3D printing with
improved printing precision plays an indispensable role in more versa­
tile structures and better mechanics that conventional manufacturing (e.
g., laminating or extrusion) cannot achieve [32].
This research studied a new 3D printing mechanism, Multiphase
Direct Ink Writing (MDIW), for fabricating alternatively layered nano­
composites along the x-y plane. The alternatively layered structure was
achieved by co-extruding two immiscible feedstocks through a specially
designed print head. The print head design was inspired by the forced
assembly method in the melt extrusion process. The forced assembly
alternatively stacks two non-compatible and immiscible polymer ma­
terials within z-axis stacked thin films for unique properties in selective
light transmission or gas barrier [28,33]. However, in this study, poly­
vinyl alcohol (PVA) and nanoparticles of multiwalled carbon nanotubes
(MWNTs) were used as examples in fabricating multiphased and
multilayered composites (along the x-y plane). Continuous ink deposi­
tion led to thin-ply structures, with mechanical properties influenced by
the layer thickness. The 64-layered structures showed much thinner
layer dimensions than the 4-layered ones (i.e., 32 µm vs. 500 µm) and
better layer distinctions than higher numbers (e.g., 256- and
512-layered structures). As a result, the 64-layered samples showed
much higher mechanical properties than the PVA (i.e., 0.74 GPa/15.45
MPa vs. 0.15 GPa/5.43 MPa for modulus/strength). Compared to the
4-layered structures with the same MWNTs concentration, the
64-layered composites were ~70% higher in modulus and ~36% in
strength. These enhanced mechanics was due to the improved layer
thickness precision, crystallization, and particle orientations. Our MDIW
showed one-step processing with a printing speed up to 1200 mm/min
with a high-precision control down to unit microns, with the most
refined printing features two orders of magnitude higher than many
inks- or gel-based 3D printing methods [17,34].
2. Experimental
2.1. Materials
PVA (i.e., PVA 28–98 with a molecular weight (Mw) of ~ 145 kg/
mol, 98–99 mol% degree of hydrolysis, and CAS # 9002–89–5) was
requested and provided by Kuraray. Dimethyl sulfoxide (DMSO)
(American Chemical Society reagent, >99.8%, CAS #67–68–5) and
methanol (>99.8%, CAS #67–56–1) solvents were purchased from
Sigma-Aldrich and used as obtained. MWNTs (NC7000 series, 90% pu­
rity, with a surface area of 250–300 m2/g and an average length and
2
Additive Manufacturing 47 (2021) 102322
diameter of 1.5 µm and 9.5 nm, respectively) were purchased from
Nanocyl. All the materials were used as received.
2.2. Material processing and manufacturing procedures
To fabricate multilayered structures and include multiple materials,
we used two different feedstock materials. Feedstock A was the PVA/
DMSO solutions, and Feedstock B was the MWNTs suspensions (i.e.,
MWNTs dispersed in PVA/DMSO) (Fig. 1a). Different PVA weights were
added to DMSO with constant mechanical stirring at 110 ◦ C for feed­
stock A (i.e., 5 wt%, 10 wt%, 15 wt%, 18 wt%, and 20 wt% PVA/DMSO).
For MWNTs suspensions, the nanotubes were first dispersed in DMSO
using a bath sonicator for 16 hrs, then 1 wt% of the polymer was dis­
solved in DMSO and bath sonicated for another 16 hrs to improve the
dispersion. Additional PVA was then dissolved in the solution using
mechanical stirring until desirable PVA concentrations (i.e., 20%, 18%,
and 15% PVA/DMSO) and MWNTs percentage (i.e., 1.0 wt%, 1.5 wt%,
and 2.0 wt% MWNTs/PVA) were achieved. The PVA/DMSO solutions
and composite suspensions were vacuum-degassed at 60 ◦ C with 30 in.
of Hg pressure for 30 mins to eliminate bubbles.
The PVA/DMSO solutions and MWNTs/PVA/DMSO suspensions
were loaded into two separate stainless-steel syringes and extruded
using syringe pumps (KDS LEGATO 200 dual syringe pumps with an
accuracy of +/- 0.35%) at 1.5 ml/min (Fig. 1b and c). Our 3D printing
platform was based on an open-source 3D printing system (Hydra 16 A
640 from Hydrorel) with a heatable and closed environment (tempera­
ture range − 50 ◦ C to 200 ◦ C). The printer has a 60 cm × 40 cm x 25 cm
build volume for x, y, and z axes, respectively. The printer has a
150 + MHz 32-bit ARM processor and modular, micro-stepping motor
drivers with closed-loop encoding. The printer has a positional accuracy
of 10 µm and a printing feature of 1 µm in the z-axis for polymer melts.
With PVA/DMSO solutions, the printing accuracy and fine feature
values were 200 µm and 50 µm, respectively, along the x-y and z axes.
Our MDIW 3D printer has unique in-house designed, manufactured,
and assembled components (Fig. 1c–f). The print head consists of four
primary parts (i) a spinneret, (ii) a minimizer, (iii) a series of layer
multipliers, and (iv) a reducer (Fig. 1f). All the parts (i–iv) were designed
using SolidWorks 2019 and manufactured using a Concept-Laser M2
metal 3D printer with Inconel 718. Inconel 718 is a precipitation-
hardenable nickel-chromium alloy containing significant amounts of
iron, niobium, and molybdenum, along with lesser amounts of
aluminum and titanium. These parts were post-processed for the solu­
tions and the suspensions to flow smoothly within the print head
channels by removing the supports and polishing exterior and interior
walls’ surfaces. These customized parts (i–iv) were connected using nuts
and bolts (Fig. 1f). Fig. 1g1 shows the printing platform, and Fig. 1g2
exhibits the print head. The number of multipliers varied depending on
the desired layer numbers to produce in the composites.
2.3. Characterization
The rheology tests were conducted via a rheometer (Discover Hybrid
Rheometer HR2, TA Instruments). The viscosity of each sample
composition was measured using a cone-and-plate geometry. The sam­
ples of 2 ml were dropped on a 40 mm, 2◦ Peltier cone steel plate. The
viscosity values were measured with varying shear rates (e.g., 0.001 /s
to 8000 /s), 100 µm truncation gap, and 50 µm trim gap offset at room
temperature. The feedstock was overfilled to avoid rheology edge frac­
ture, with the excess solutions being removed before beginning each
run. Each sample was tested three times to prevent system errors. The
rheological behavior of layered structures was also tested via plate-and-
plate geometry. The 8 mm disposable aluminum parallel plates were
used to study the variation in viscosity and stress as a function of ma­
terial layer numbers within varying shear rates (0.01 /s to 1000 /s). The
study was conducted with a geometry gap of 100 µm between the par­
allel plate at room temperature. The multilayered morphology was
D. Ravichandran et al. Additive Manufacturing 47 (2021) 102322

Fig. 1. (a) The feedstock preparation with material A as polymer solutions and B as MWNTs suspensions, (b) loading the feedstock into separate syringes, (c) two
syringe pumps with programmable feeding as extrusion systems, with a computer system for the material writing path control to additively manufacture (d)
alternatively-layered, mesostructured patterns along the x-y plane with digital images of the printed samples (i.e., nanomaterials, microlayers, and macro laminates)
(scale bar: 2 mm), (e) system configuration of our 3D printing platform, (f) the critical print head design composed of four components (i.e., the spinneret, minimizer,
layer multiplier, and reducer), photos of the (g1) in-house printing platform, (g2) print head assembly corresponding to the design in (f), and (g3) printing of one
individual line with multilayered structures and textures observed on the XY plane.

observed using an optical microscope (OM) (Nikon eclipse E200 and
Olympus MX50) to identify the size and number of layers for individu­
ally printed lines. Raman spectroscopy analysis (Raman spectrum and
Raman mapping) was conducted using confocal Raman-AFM micro­
scopy (WITec alpha 300 RA) with a 532 nm laser to detect the MWNTs
VV configuration. The samples were scanned at 0◦ and 90◦ for each
polarized angle with a fixed laser polarization configuration. A Differ­
ential Scanning Calorimetry (DSC) (Discovery DSC 250, TA Instruments)
was performed with a modulated mode, from room temperature to
280 ◦ C at 5 ◦ C/min temperature ramp for a sample size of ~10 mg. The
temperature modulation was 2 ◦ C for 60 s. X-ray diffraction (XRD) was
conducted using an Aeris X-ray diffractometer (Malvern Panlytical) from
5◦ to 70◦ for a period of 15 mins at 0.09◦ /s. The tensile test was con­
ducted with a tensile tester (Discover Hybrid Rheometer HR2, TA In­
struments) at room temperature with a constant linear rate of 100 µm /s.
The tension gauge length was 15 mm long for samples with a thickness
of 200–250 µm, measured using an optical microscope (Olympus
MX50). The printed materials showed high tensile strains, and a smaller
gauge length (e.g., ~2 mm) was used to show some samples’ fracture
behaviors. The samples were air-dried for one day and kept in the
desiccator for another 24 hrs to remove the solvent residue before
conducting all tests (e.g., mechanical testing, Raman, DSC, XRD).
3. Results
3.1. The rationale of our new additive manufacturing for multilayered
structures
Our in-house developed 3D printing platform reported here has been
optimized to produce high quality prints feature at maximum speed
(Table S1) without sacrificing the phase domain size in 3D printing. The
control of these phase domain size is essential in our application of
layered structures, as this printing feature will determine the distribu­
tion of nanoparticles and their reinforcement effects. The MDIW has a
printing speed of ~1200 mm/min and a printing feature size as low as
~4 µm, two orders of magnitude better than many reported printing
features (Table S1). Fig. 1 shows the printing platform and the layer
multiplication mechanism in our MDIW 3D printing. Two materials,
Feedstock A of the PVA/DMSO solutions and B of MWNTs suspensions
(Fig. 1a), were filling two syringes (Fig. 1b) and transported via the
syringe pumps to the print head (Fig. 1c). Unlike conventional DIW, our
3D printing can produce layered microstructures containing alternating
compositions along the x-y plane within each printing line or layer (i.e.,
polymer and nanoparticle content in alternating layers, as shown in
Fig. 1d). The microlayers and macrolayers printed via our MDIW
method are feasible through solidification processes (Fig. 1d). This
research will focus on the thin-ply materials as they are basic building
blocks for more complex structures. Furthermore, the MDIW-printed
individual microlayers containing confined nanotubes are scalable for
thin-ply and laminates, blending the top-down (i.e., from the filament to
submicron layers) and bottom-up (i.e., from the filament to thin-ply to

3
D. Ravichandran et al. Additive Manufacturing 47 (2021) 102322

laminates) protocols in one procedure (Fig. 1d).
The MDIW has six major components, namely, (i) the machine
controls for deposition sites, (ii) injection controls via the syringe
pumps, (iii) reservoir syringes containing feedstock A/B, respectively,
(iv) delivery tubes for the transportation of the feedstock to the print
head, (v) in-house developed print head and (vi) the printed object on
the printing substrates (Fig. 1c–e). Among these components, the print
head’s unique design and assembly were the most important in
achieving mesoscale, multilayered structures (Fig. 1f). Feedstock A (i.e.,
PVA/DMSO solutions) and B (i.e., MWNTs/PVA/DMSO suspensions)
entered the spinneret, minimizer, layer multipliers, and a reducer
component of the print head. A minimizer was used between the
spinneret and the layer multiplier unit to reduce the flow area and in­
crease the shear for layer formations without any flow disturbance (e.g.,
feedstock temperature, viscosity, flow rate, and internal smoothness of
the print head). Feedstocks A and B were split horizontally within each
multiplier, stacked, and stitched vertically to form alternating layers of
both the feedstocks (Fig. 1f). In this way, having one multiplier attached
to the spinneret produced four alternating layers. Similarly, the number
of n multipliers will generate alternating layers in the order of 2 n+1
along the printing line direction. In this way, the 3D printing speed in a
unit of ml/min will depend on the nozzle dimensions. Simultaneously,
the nozzle size increase does not sacrifice the printed phase domain size
determined by the multiplier numbers instead of the printing head

Fig. 2. Rheology study for shear rate effect on viscosity and stress for (a1-a4) varying weight percentage of PVA in DMSO solutions/solutions (feedstock A); (b1-b4)
15 wt% PVA/DMSO with different concentrations of MWNTs (feedstock B); (c1-c4) 18 wt% PVA/DMSO with varying concentrations of MWNTs (feedstock B). (a1, b1,
c1) viscosity vs. shear rates, (a2, b2, c2) shear stress vs. shear rates, (a3, b3, c3) viscosity at the different shear rates with (a3) determining the PVA/DMSO concentration
to be 20 wt% and (b3-c3) optimizing the 1 wt% CNT concentration in 18 wt% PVA/DMSO for viscosity matching and layer integrity in 3D printing; (a4, b4, c4)
structural stability of printed lines with varying PVA and MWNTs.

4
D. Ravichandran et al.
design (Fig. 1f). A reducer functions as a regulator to modify the fila­
mentary shape and cross-section size. The printed objects were dried for
respective property tests with proper solvent exchange followed by
proper post-treatment (i.e., air dry in a desiccator for 24 h to eliminate
residue solvent). Fig. 1g1-g3 exhibited the printing platform, print head
installation, and direct writing on the printing platform, with the
multilayered structures fabricated.
3.2. Printability and layer formability
It is essential for direct writing-based 3D printing to form shear-
thinning behavior for the inks not to clog during deposition. Upon
exiting the printing needle, the solutions would develop viscoelastic
properties for the printed objects to maintain their structural integrity.
Regarding our layered structure, controlling the viscosity and viscosity
matching between layers was critical for layered structures. Fig. S1
shows the effect of viscosity on layer formation stability. It is crucial to
have a minimal viscosity difference between the feedstock to form stable
layers and interfaces. Fig. S2 gives examples of non-uniform layer for­
mation due to viscosity mismatch between the feedstocks. Fig. 2 showed
the viscosity of polymer solutions and nanotube suspensions. With
increased polymer content in Feedstock A, the PVA/DMSO solutions
displayed increased viscosity (Fig. 2a1). The 20 wt% PVA/DMSO
showed the highest viscosity of ~30 Pa.s at a shear rate of 10 /s
(Fig. 2a1-a3). Linear viscoelastic region (LVER) defined the linear shear
stress-shear strain region (i.e., between the shear rates of 0–100 /s in
Fig. 2a2). The 5 wt% PVA/DMSO showed the longest LVER due to its
dilute regime with the least entangled polymer chains and the poor
structural stability. The 20 wt% PVA solutions showed the shortest
LVER, beyond which a pseudoplastic region appeared due to molecular
reorganizations with distinct shear-thinning benefiting 3D printing
procedures. Fig. 2a4 shows the structural stability and flow character­
istics of varying PVA concentrations, with 20 wt% PVA showing the best
printability.
A narrow viscosity gap or close viscosity matching between Feed­
stock A and B is critical to avoid layer breakage during printing.
Therefore, the Feedstock B content was delicately designed, considering
that the inclusion of MWNTs would increase the viscosity. A percentage
of 15 wt% and 18 wt% of PVA were prepared and tested with different
MWNTs loading, respectively (Fig. 2b and c). Compared to 15 wt% pure
PVA (Fig. 2a1-a3), 1 wt% MWNTs addition did not change the viscosity
much (Fig. 2b1). The PVA solution and MWNTs suspension samples
showed a viscosity of ~10 Pa.s at a shear rate of 10 /s. Higher MWNTs
content increased the viscosity, e.g., up to 15 Pa.s at a shear rate of
1–100 /s at the MWNTs concentration of 2 wt% (Fig. 2b1-b3). However,
these MWNTs suspensions showed a lower viscosity than the 20 wt%
PVA/DMSO across the entire shear procedure (Fig. 2a1-b1). This
microstructural instability would cause layer breakage during multi­
plication procedures, thus making it undesirable. Fig. 2b4 shows the
structural stability and flow characteristics of varying concentrations of
MWNTs in 15 wt% PVA/DMSO.
The 18 wt% PVA with varied MWNTs content showed a similar LVER
to the pure polymer solutions (Fig. 2c1). Like the 15 wt% PVA, the
addition of the MWNTs in 18 wt% PVA did not disrupt the polymer
chain networks (i.e., linear shear stress-rate relationship in Fig. 2c2).
This microstructural stability was due to the polymer chain entangle­
ments that would also retain their dimensional consistency after printing
on the substrates (Fig. 2c2) [35–37]. The MWNTs content increased the
viscosity of the 18 wt% PVA stably within the LVER (<200 /s) (e.g., 1 wt
% MWNTs increased the viscosity to ~25 Pa.s, 1.5 wt% MWNTs
increased to ~32 Pa.s, and the 2 wt% MWNTs increased to ~37 Pa.s at a
shear rate of 10 /s) (Fig. 2c3). Fig. 2c4 also shows the structural stability
and flow characteristics of these composite solutions. Other composi­
tions, such as a higher concentration of MWNT (>2 wt%) in lower
polymer solutions (<15 wt%), can be compatible with our unique 3D
printing method. This study only used 20 wt% PVA/DMSO and 1 wt%
5
Additive Manufacturing 47 (2021) 102322
MWNT/18 wt% PVA/DMSO to demonstrate our MDIW printability and
the composite properties; other compositions with similar viscosity may
also find it feasible to print similar layered composite structures.
The feedstock rheology measured from the cone-and-plate geometry
provided viscosity values under uniform shear (Fig. 3a). The Feedstock A
(i.e., 20 wt% PVA/DMSO) and Feedstock B (i.e., 1 wt% MWNTs in 18 wt
% PVA/DMSO) displayed matched viscosity (Fig. 3b1 and b2). For
further understanding the layer interactions in the printing procedure,
the multiplication process was mimicked in the rheology tests using a
plate-and-plate geometry (Fig. 3c) [38,39]. The PVA/DMSO and
MWNTs/PVA/DMSO were stacked on top of each other in different
layers and tested compared to homogeneous solutions. The layers were
produced on top of each other simply by attaching the layer multipliers
in reverse to the spinneret. The viscosity and shear stress as a function of
shear rate was shown in Fig. 3d1/d2 and 3d3/d4, respectively. The 20 wt
% PVA displayed the highest viscosity, e.g., ~43 Pa.s between a shear
rate of 10-1-30 /s, ~10 Pa.s higher in the plate-and-plate geometry than
the cone-and-plate measurement (Fig. 2a1, a3) due to the shear stress
distribution differences among these two measurement setups.
The 1 wt% MWNTs/18 wt% PVA/DMSO mixtures showed the lowest
viscosity due to nanotubes’ lubrication effect [40–42]. The 8-layered
composites showed lower viscosity than the pure PVA (Fig. 3d1, d2).
The increased layer numbers further decreased the friction among
layers, e.g., 36 Pa s for 8 layers, 32 Pa s for 32 layers, and 30 Pa s for 64
layers at a shear rate of 10 /s. The interfacial lubrication due to MWNTs
diffusion between layers contributed to the friction decrease. However,
the increase of layer numbers to 256 and 512 layers showed increased
viscosity of 33 Pa s and 34 Pa s, respectively. This viscosity increase was
attributed to nanotube dispersion difficulty that disrupted the layer
structures and possibly more polymer chain entanglement as a result of
diffusion at the layer interfaces. All the stacked layers showed similar
LVER, which was necessary to maintain layer stability (Fig. 3d3/d4).
Fig. 3e1-e4 explain the layer formation and the associated shear rates
due to increasing layers (i.e., layer number 1–512, with the 1-layered
structure for the pure polymer printing). The two feedstocks entered
two separate channels of the spinneret at 1.5 ml/min (i.e., 25 mm3/sec)
(Fig. 3e1), forming a side-by-side stacking (i.e., 2 layers in the mini­
mizer, Fig. 3e2). The multiplier has three parts, the inlet, the outlet, and
the central part called the divider, which helps the layer stacking in the
multiplication mechanism. The multiplier has a horizontal divider at the
inlet that divides the incoming two layers and flows into four quadrants.
The divider’s function is to divert the flow to stack the individual
quadrants side-by-side and arrange them side-by-side in the x-y plane
when exiting the outlet (Fig. 3e3). The following equations give the
shear rate of an individual layer entering each multiplier channel.
v
γ= (1)
w
Vo Vo
v= = (2)
A hw/n
γ=
Vo n
(3)
w2 h
Here γ is the shear rate (/s), v is the flow velocity (mm/s), h is the
channel height (mm), Vo is the volume flow rate of the feedstock
controlled by the feeding system (mm3/s), w is the channel width (mm),
and n is the number of multipliers. The height and width of each channel
in the multiplier are 5 mm, respectively. Fig. 3e4 showed the calculated
shear rate as a function of the layer number, with 512-layered structures
showing a shear rate of ~100 /s upon entering the 8th multiplier. The
calculated shear rates showed the flow behavior consistency between
feedstock A and B (Fig. 3b1 and b2), confirming the printing stability.
D. Ravichandran et al. Additive Manufacturing 47 (2021) 102322

Fig. 3. (a) Cone-and-plate geometric rheology setup for absolute viscosity measurement; (b1-b2) viscosity and stress vs. shear rate matching between feedstock A and
B; (c) plate-and-plate geometric rheology setup for the layered structure measurement, (d1 & d3) viscosity and stress for pure feedstocks and layered composite
solutions (i.e., 8–512 layers); (d2 & d4) zoom-in regions of viscosity (d1) and stress (d3); (e1-e3) multiplier dissembling showing the multiplication procedure for the
(e4) shear rate calculation.

6
D. Ravichandran et al.
3.3. Structure and morphology studies
Composites with different layer numbers were manufactured via the
MDIW, as shown in Fig. 4a. The reducer component in the print head
(Fig. 1f) determined the width and thickness of an individually printed
line (i.e., 2 mm in width and 200 µm in thickness for one printing line).
The MDIW successfully prepared composites with a layer number of 4, 8,
16, 32, 64, 256, and 512 (i.e., the white regions were the PVA and the
black regions are the MWNTs/PVA layers). Fig. 4b shows an example of
the as-printed thin-ply structures with continuous printing lines, with a
total ply size of 100 mm × 80 mm and 16 layers in each printing line.
The as printed ply structure had an average layer thickness of
~164.6 ± 26.5 µm after 1 min of completion of the print, and
~184.6 ± 15.3 µm after three hours of completion of the print. The
layered structures exhibited high structural integrity and stable texture
during a 3 hrs exposure to air. Our adoption of the solvent exchange-
based gelation immediately fixed the shape and dimensions of printed
structures, thus providing a higher-precision printing feature than these
air-exposed samples.
The as-obtained MWNTs in DMSO suspensions showed high aggre­
gates (Fig. 4c1) and 1 wt% PVA/DMSO addition in the MWNT suspen­
sions much improved the dispersion quality (Fig. 4c2). The eventual
MWNTs in feedstock B exhibited comparatively uniform MWNTs dis­
tributions (Fig. 4c3), with random aggregates at a scale of 10 µm
(Fig. 4c4). These aggregates made processing a higher layer number than
512 (i.e., layer thickness at nanometers) challenging due to our
simplified processing of nanotube dispersions, e.g., via a short-period
sonication. The layer thickness values were calculable from the multi­
plications compared to the experimental measurements (Fig. 4d). This
comparison showed a high consistency between the experimental design
and the real layer dimensions, with the 512-layered structures showing a
single layer size of ~4 µm. The 4-layered composites showed a layer
thickness of ~500 µm and the 64 layered samples exhibited a thickness
of ~45 µm, a printing feature already higher than most DIW 3D printers
(e.g., > 200 µm) [14,43]. Based on the optical images (Fig. 4a) and
image analysis (Fig. 4d), composites with less than 64 layers showed
distinct layers while the 256/512 layers displayed textured morphology.
The increasing layer numbers also improved the layer consistency,
Fig. 4. (a) Optical images of 4–512 layered structures (scale bar of 500 µm); (b) an example of structural stability of as-printed 16-layered structures; optical images
of (c1) MWNTs/DMSO dispersions after simple sonication; (c2) effects of 1% PVA on MWNTs dispersions; (c3-c4) MWNTs dispersion in the final PVA/DMSO feed­
stock; (d) layer size from the experimental and theoretical calculations.
7
Additive Manufacturing 47 (2021) 102322
corresponding to more stabilized printing width and layer width
(Fig. 4d). Fig. 5a-b showed the higher-precision printing feature images
of layer dimensions in 256- and 512-layered composites.
3.4. MWNT alignment and layer-layer interactions
Raman analysis was conducted on the as-printed samples to find the
preferential alignment factor. MWNTs nanomaterials have the depo­
larization effect, and Raman spectra can reflect their orientation and
distribution quality. Fig. 6 shows the 64- and 256-layered structures as
the layered samples were placed with different laser-layer angles (i.e.,
θ = 0◦ in Figs. 6a1-a2, 5b1-b2, and θ = 90◦ in Fig. 6a3-a4, b3-b4). It was
challenging to perform Raman mapping for layer numbers smaller than
64 layers due to the larger layer size (i.e., >50 µm) than the polarization
laser spot size (i.e., 1.2 µm). The Raman modes in the VV configuration
exhibit a maximum intensity when the incident light is polarized in the
longitudinal axis (i.e., along with the layered structures) (Fig. 6a1-a2),
while the Raman intensity is significantly suppressed when the laser is
polarized in the lateral axis (i.e., perpendicular to the layer directions)
(Fig. 6a3-a4) [44–47]. The color mapping (Fig. 6a2, a4, b2, b4) reflected
the MWNTs conformation variations and their corresponding intensity
spectra were plotted (Fig. 6a1, a3, b1, b3).
MWNTs have feature peaks of the D- and G-bands at 1353 cm− 1 and
1580 cm− 1, respectively [48]. The 64-layered structures at
θ = 0◦ (Fig. 6a1-a2) showed the PVA layers colored in purple with fewer
MWNTs diffused, PVA/MWNTs layers colored in green (i.e., both light
green and dark green), and the distinct interfaces colored in red. The red
color suggested the highest intensity, with a uniform distribution at the
interfaces when θ = 0◦ , but the green color with the lowest intensity in
the PVA/MWNTs layer appeared at interfaces when θ = 90◦ (Fig. 6a2 vs.
a4). Based on the dependency of the MWNT signature peaks on polari­
zation angles, such observation indicated superior nanotube alignment
at the interfaces comparing to the inner region of the MWNTs/PVA
layer. Furthermore, with an increase in the layer numbers (i.e., 4–64),
the interfacial area increased and contributed to better MWNTs
alignment.
The 256-layered structures showed less than 10 µm-thick PVA layers
(i.e., colored in purple in Fig. 6b2) in Raman mapping, consistent with
D. Ravichandran et al. Additive Manufacturing 47 (2021) 102322

Fig. 5. (a) 256-layers with the (a1) cross section (100x), zoom in regions of (a2) 400x & (a3) 1000x; (b) 512-layers with the (b1) cross section (100x), zoom in regions
of (b2) 400x, (b3) 1000x.

Fig. 6. Raman mapping of the 64 layers and 256 layers film. Averaged Raman intensities of the D-band and G-band for 64 layers film at (a1) θ = 0◦ and (a3) θ = 90◦
and their corresponding Raman mapping in (a2) and (a4), with distinct alternating layers; averaged Raman intensities of the D-band and G-band for 256 layered
structures at (b1) θ = 0◦ and (b3) θ = 90◦ with corresponding Raman mapping in (b2) and (b4), with alternating layers of PVA and PVA/MWNTs.

the OM observation and theoretical calculations (Fig. 4d). As compared
to the 64-layered structures, the 256-layered structures showed much
stronger MWNTs diffusion into the PVA regions (Fig. 6b2 vs. a2). The
enhanced D-band and G-band intensities also indicated a diffusion of the
MWNTs between the layers blurring the interfaces (Fig. 6b1-b2). The
diminished interface deteriorated the interfacial alignment effect
observed for the 64 layers. The θ = 0 ◦ (Fig. 6b1-b2) peak intensity
observed little difference between the layer interface and the layer core
regions for the 256-layered MWNTs/PVA regions (Fig. 6b3-b4). The ratio
of averaged intensities between θ = 0◦ and θ = 90◦ , I0/I90, is usually a
facile indication of preferential orientations [49]. I0/I90 ratio of the
D-band for the 64 and 256 layers was calculated to be 2.17 and 1.71,
respectively, indicating a higher angular dependency for the 64 layers,
thus a better MWNTs alignment.
To better understand the MWNTs orientation, 64-layered composites
containing PVA and PVA/MWNT in alternating layers were compared
with a D-phase composite, i.e., composites containing MWNTs/PVA
across the entire cross-section (Dm, where m is the number of layers).

8
D. Ravichandran et al. Additive Manufacturing 47 (2021) 102322

The D-phase composite (D64) was fabricated using the same printhead
configuration as the 64-layered composites but with feedstocks A and B
of the same composition of PVA/MWNTs. A single spectrum Raman
analysis was performed (Fig. S3). The I0/I90 ratio of the D-band for D64-
phase and 64-layered composites had comparable values of 2.07 and
2.17, respectively, demonstrating the multipliers’ facilitation in
improving the MWNTs alignment.
3.5. Crystal structure analysis
3.5.1. Modulated differential scanning calorimetry
MDSC was used to detect the composites’ crystallization behavior
and layer numbers’ influence on the crystal formation (Fig. 7a1). A
couple of melting peaks appeared in samples and the weaker melting
was indicated with arrows (i.e., ~170–200 ◦ C, Fig. 7a1). The two
melting peaks suggested two primary polymer crystals of different sizes
[50,51]. The lower temperature peak (Tm1, 175–190 ◦ C) was associated
with a smaller enthalpy for melting the smaller crystal size and the
higher temperature peak (Tm2, 220–250 ◦ C) with a larger enthalpy for

Fig. 7. Modulated Differential Scanning Calorimetry (MDSC) curves for the (a1) normalized total heat flow curves and (a2) peak melting temperatures of lower (Tm1)
and higher exotherm (Tm2); XRD measurements of the (b1) peak fitting of principal crystal planes, (b2) crystallinity and crystal sizes, and (b3) d-spacing for (101) (2θ
~ 19.87◦ ) and (001) (2θ ~ 16.08◦ ).

9
D. Ravichandran et al. Additive Manufacturing 47 (2021) 102322

the bigger crystal size. These two melting temperatures were plotted in
Fig. 7a2. The influences of layer numbers on the two melting peaks were
consistent. With the increase of the layer numbers from 4–64 layers, the
melting temperatures approximately decreased due to more interactive
interfaces [52]. However, the lack of uniform layers in the 256- and
512-layered structures disrupted the MWNTs distributions and orien­
tations (Fig. 6b1-b4) and led to varied transition temperatures. Table 1
listed the enthalpy, crystallinity, and primary crystal size. The degree of
crystallinity (Xc) was obtained via the following equation [53–55].
∆H
Xc = × 100 (4)
∆Hc
Here ΔH is the melting enthalpies obtained from the normalized heat
flow curve (Fig. 7a1), and ΔHc is the enthalpy for 100% crystalline PVA,
161 J/g [56,57].
The crystallization peak of the semi-crystalline polymer reflected the
crystal size variation, relevant to their responses to the temperature
sweeping (Fig. 7a1). The larger the crystal size, the higher the melting
peak; the narrower the size distribution, the smaller the full-peak-width
at half maximum. The averaged lamellar thickness (Lc) can be calculated
based on the following Gibbs-Thomson equations [58–60].
2σ
Tm = T om (1 − ) (5)
∆Hm L
2σ Tm◦
L= (6)
∆Hm ((T om − Tm )
Here Tm is the measured melting temperature for a given lamellae
thickness L, Tmo is the equilibrium melting temperature of an infinitely
thick crystal (i.e., 249 ◦ C [61,62]), σ is the surface free energy per unit
area of the crystal basal plane (i.e., 37.2 × 10− 3 J/m3 [63]), and ΔHm is
the enthalpy of fusion per unit volume (i.e., 166.3 × 106 Jm− 3 [64,65]).
The calculated values of crystallinity (Xc), and lamella thickness (L),
along with melting temperature (Tm) were included in Table 1.
The crystallinity at the low-temperature exotherm (Tm1, 175–190 ◦ C)
was between 20% and 37%. PVA showed the lowest crystallinity at
19.28%, and the layered samples showed increased crystallinity. The
corresponding crystal size also increased from 3.19 nm in PVA to a range
of 3.80–4.14 nm in the composite layers (Table 1). The smaller crystals
may have formed due to the breakup of small grains/clusters caused by
shear forces during the layer formation process and confinement effects
[66,67]. The higher exotherm (Tm2, 220–250 ◦ C) indicated much larger
crystals, with the size varying 7–19 nm than that for the
low-temperature exotherm (i.e., 3–5 nm). The melting temperatures
(Tm2), crystallinity (Xc2), and crystal size (Lc2) dropped from the pure
PVA to the composite layers (Table 1). The crystal sizes calculated here
were the average of different crystal planes. Thus, the XRD data may
clarify the crystallinity and crystal size variations in specific crystal
planes.
3.5.2. X-ray diffraction
XRD spectra (Fig. 7b1) provided the crystallinity (Xc_XRD), crystal size
(LXRD), and the d-spacing for the interplanar distance (d) based on the
following equations.
Ac
Xc_XRD = (7)
Ac + Aa
kλ
LXRD = (8)
βCosθ
2dSinθ = nλ (9)
Here Ac is the crystalline peak fitting area, Aa is the amorphous peak
fitting area, λ is the X-ray wavelength, θ is the Bragg’s angle, β is the
angular full-width-at-half-maximum (FWHM) intensity, n is 1, and k is a
constant with a value of 0.9 [68,69]. The diffraction peaks were
observed at 2θ angles ~ 16.08◦ , 19.87◦ , and 41.11◦ corresponding to
crystal planes of (001), (101), and (111) (Fig. 7b1). The amorphous peak
was observed at 2θ angles ~22.76◦ (Fig. 7b1). These crystal planes were
fitted based on lattice contestants of a = 7.81 Å, b = 2.52 Å, c = 5.51 Å,
and β = 91◦ 42′ for an optimized monoclinic structure of PVA [70,71].
The crystallinity, crystal sizes, and d-spacing calculated using the
XRD spectra after peak fitting are tabulated in Table 2 and represented
in Fig. 7b2-b4. There was a crystallinity increase from the PVA
(~32.37%) to the layered composites (~40–44%), with 64 layers
showing the highest crystallinity (43.95%) among the layered composite
(Fig. 7b2). However, the layer numbers did not affect the crystallinity
significantly (Table 2). The high crystallinity in the layered composites
was possibly due to higher polymer chain confinement and nanotube
nucleation effects within each layer. A reverse trend was observed in
cases of crystal size and d-spacing from PVA to layered composites. The
crystal sizes from two planes (i.e., 101 (2θ ~ 19.87◦ ) and 001 (2θ ~
16.08◦ ) along b-axis) influence the PVA mechanics the most because of
their alignment along the tension direction [65]. PVA showed the largest
crystal size in both the planes (i.e., 5.53 nm for (101) and 3.221 nm for
(001)). In comparison, the layered composites had a crystal size of
2.390–2.676 nm in the (001) and 4.310–4.985 nm in the (101) planes.
The smaller d-spacing in layered composites also suggested more closely
packed crystals (Fig. 7b3). The smaller crystal size (e.g., based on the
Hall-Petch relationship) and d-spacing (e.g., higher close packing) usu­
ally lead to higher material strength [72].
3.6. Tensile Test
The PVA and composites as-printed showed high stretchability with
strain values quickly exceeding the general tensile tester capabilities (e.
g., >2000% strain). Thus, these samples were first tested with a gauge
length of 15 mm with a tensile strain of 30%, only to expose the elastic
regions (Fig. 8a and Table S2). Fig. 8a shows Young’s modulus and ul­
timate tensile strength (UTS) for pure PVA and multilayered composites.
With the same MWNTs concentration (i.e., 1 wt% or 0.5 vol%), the
layered composites displayed modulus and strength values with high

Table 1
MDSC analysis of composites containing 4–512 layers film and PVA film.
Layers Heating Cycles in the MDSC tests

Tm1 (◦ C) Tm2 (oC) ΔH1 (J/g) ΔH2 (J/g) Xc1 (%) Xc2 (%) Lc1 (nm) Lc2 (nm)

1 (PVA) 175.70 236.69 31.04 67.01 19.28 41.62 3.19 18.98

4 192.63 233.93 59.00 57.88 36.65 35.95 4.14 15.50
8 187.93 222.69 51.35 61.82 31.89 38.40 3.83 8.88
16 182.53 220.23 54.62 63.57 33.93 39.48 3.51 8.12
32 186.83 223.86 59.14 64.08 36.73 39.80 3.76 9.29
64 181.31 223.94 45.06 68.92 27.99 42.81 3.45 9.32
256 187.55 218.44 49.43 64.56 30.70 40.10 3.80 7.64
512 188.01 246.05 32.54 56.57 20.21 35.14 3.83 N/A

Note: The enthalpy for the fully crystallized PVA polymers is 161 J/g [56,57].

10
D. Ravichandran et al. Additive Manufacturing 47 (2021) 102322

Table 2
XRD analysis of composites containing 4–512 layers films and PVA film.
Layers Xc_XRD (%) LXRD (nm) d (nm)

(101) (2θ ~ 19.87 )

◦
(001) (2θ ~ 16.08 )
◦
(101) (2θ ~ 19.87◦ ) (001) (2θ ~ 16.08◦ )

1 (PVA) 32.37 5.531 3.221 0.2295 1.7708

4 41.97 4.985 2.464 0.2280 1.3548
8 43.03 4.372 2.461 0.2289 1.3533
16 43.23 4.702 2.461 0.2283 1.3533
32 40.54 4.677 2.483 0.2294 1.3653
64 43.95 4.763 2.448 0.2283 1.3463
256 42.17 4.727 2.390 0.2282 1.3262
512 41.82 4.310 2.676 0.2300 1.4718

Xc_XRD, crystallinity from XRD; LXRD, crystal size from XRD fitting; d, d-spacing or the crystal plane distance from XRD fitting.

Fig. 8. (a) Young’s modulus and ultimate tensile strength vs. layer numbers; (b) E30% strain vs. layer numbers; stress-strain curves of (c) all the samples at a 15 mm
gauge length; (d) selected samples at a 2.5 mm gauge length to show the fractures; (e) photos tensile setup at max limit of the machine for 2.5 mm gauge length.

dependence on the layer numbers (Fig. 8a and Fig. S4). Pure PVA
showed the lowest modulus (0.145 ± 0.035 GPa) and strength
(5.44 ± 0.72 MPa). In comparison, the 64-layered structures showed ~5
times higher modulus (0.737 ± 0.082 GPa) and ~3 times higher
strength (15.45 ± 0.87 MPa), suggesting the MWNTs’ reinforcement
effect of ~ 240 GPa for modulus and ~ 4 GPa for strength, respectively,
based on simple composite mechanics rule-of-mixture (Eq. 10) [73–75].
The corresponding reinfnorcement efficiency factor is calculated 16.33
[76]. Though smaller than the intrinsic values of MWNTs (i.e., Young’s
modulus ~500–1000 GPa and strength ~20–100 GPa, respectively)
[77,78], the MWNTs materials in our study were dispersed only in
simple sonication and involved aggregates in the layered structures. The
consistent increase of modulus and strength from pure PVA to 4-layered
to 64-layered structures was primarily due to thinner layer thickness and
more interactive interfaces [38]. The constant MWNTs concentration
among different composites does not influence the reinforcement ef­
fects. However, the 64-layered structures showed preferential nanotube
alignment (Fig. 6a1-a4) along the axial nanotube direction, much

11
D. Ravichandran et al.
enhanced the composite mechanics (i.e., Halpin-Tsai model [79]). Note
that the composites displayed even better composite mechanics when
these MWNTs dispersed across the printing area (Table S2, D4 vs. 4, and
D64 vs. 64), considering their similar nanotube alignment (Fig. S3).
Ec = Em V m + Ef V f (10)
The 256- and 512-layered structures showed a slight decrease in
averaged modulus and strength values (Fig. 8a). Also, the standard de­
viations during the tension tests were more significant than the 64-
layered structures. The thinner layer thickness resulted in more homo­
geneous MWNTs distributions. However, Raman analysis has shown
interlayer diffusion and the less orientated MWNTs than the 64-layered
structures (Fig. 6b1-6b4). The energy absorption was calculated based on
a tension of 30% (E30% strain) showed the same trend, with the 64-layered
structures displaying the highest E30% strain capability during tension (i.
e., 3.5 times increase from PVA to the 64-layered structures, as shown in
Fig. 8b). The typical tension curves up to 30% strain and a gauge length
of 15 mm were in Fig. 8c. However, none of the samples showed a
fracture due to the samples’ super stretchability. A much-reduced gauge
length of ~2.5 mm was used to demonstrate the fracture resistance of
our 3D printed layer structures (Fig. 8d). The PVA fractured ~1500%,
and the 32-layered structures failed at ~1550%. However, the
maximum displacement of 2000% did not break the samples with a
higher layer number than 64, showing their high fracture resistance and
E30% strain (Fig. 8d). A smaller gauge length than 2 mm may get the 64-
layered structures fractured, but the stress concentration effects would
cause the breakage at the clamping point, and thus, these fracture tests
were not done. The acquired mechanical properties of our PVA/0.5 wt%
MWNTs were compared with other similar studies in PVA/CNT-based
composites (Table S3). Our demonstration of the layered composites
showed the highest mechanics improvement, namely, a maximum of
~408% increase in modulus and a ~184% increase in strength, as
compared to the general modulus improvement up to ~121% for
modulus and ~133% for strength from other studies [80,81]. The
MDIW-enabled layer structures in composite samples provided high
packing factor and alignment of nanotubes within each layer (Fig. 6 &
Fig. S3) and facilitated the stress transfer efficiency from CNTs to
polymers, rendering high mechanical property enhancement (Fig. 8).
4. Discussions
Conventional DIW mainly consists of filamentary- and droplet-based
3D printing [7,82]. Printable inks typically formulate from polymeric
species dissolved in a solvent and particulate powder suspended in a
liquid. However, simultaneous patterning of phase-distinct polymer and
nanoparticle materials, especially for sub-10 µm printing features, has
been challenging and currently limited to slow printing methods, such as
aerosol- and electrohydrodynamic jet-based 3D printing. These
high-precision and multi-material printing methods will require (i)
low-concentration nanoparticle jetting and/or (ii) multiple tiny
needle-diameter print heads. The former usually involves PolyJet or
MultiJet, with a significant challenge in rheology control and printing
nozzle clogging, lowering material deposition speed [83]. The latter
route faces difficulty in position calibration among different printing
nozzles [84]. Besides, the inter-phase material diffusion following
time-lagged, line-after-line writing would also disrupt printing features.
Considering die-swell, a unique phenomenon of polymer expansion
upon exiting the printing nozzle, the DIW printing features are usually
with a more extended printing line width than the nozzle diameter,
assuming the ink deposition without stretching (e.g., translation speed
slower than the ink flow speed) [85,86]. For example, with appropriate
polymer concentrations (e.g., a broad viscosity range of 0.1–103 Pa.s
[87]), a 100 µm-diameter can generate up to 200 µm-width lines, with a
manufacturing speed scale at 20 mm/s [88,89]. Our MDIW method has
shown an effective protocol via the unique design of the printhead to
achieve fine printing features within individual printing lines.
12
Additive Manufacturing 47 (2021) 102322
Successful printing of fine features (e.g., phase domain size) relies on
the delicate design of manufacturing parameters (e.g., rheology, nano­
particle dispersions). The printing inks showed distinct shear-thinning
behavior to avoid printhead clogging (Fig. 2a). A careful material con­
tent design (i.e., 20 wt% PVA and 18 wt%PVA/1 wt% MWNT) matched
viscosity values between layers mandatory to avoid layer breakup or
diffusion (Fig. 2c). The layered stacking of the printing inks for rheology
tests also showed a consistent trend that the layered structures have a
lower viscosity than the pure PVA, facilitating the shearing during the
multiplying procedure (Fig. 3). With good dispersion quality, layered
microstructures with different layer numbers (e.g., 8, 32, 64, 128, 256,
and 512) were prepared (Fig. 4a–b). The 64-layered structure showed
the best layer consistency and nanotube distributions because of the
observed scattering appearance of carbon nanotube aggregates in 256-
and 512-layered composites.
Nanoparticle in any form (nanotubes, nanofibers, nanorods, and
nanoribbons) displays anisotropy and shows improved mechanical or
physical properties with better dispersion and alignment [90]. This
desirable dispersion is also essential to achieve theoretically predicted
properties of the nanoparticles for high-performance applications (e.g.,
supercapacitors, sensors, actuators, heat exchangers, and biomedical
devices [91–93]). Carbon nanotubes (CNTs) are 1D nanoparticles and
display anisotropy with better performance along the tube’s axis [94].
Therefore, good dispersion and alignment of the tubes along the tube’s
axis will improve the respective properties for achieving the best per­
formance [95].
The Raman analysis showed preferential alignment of MWNTs along
the printing direction, with a higher value orientation factor in the 64
layers than the 256 layers (Fig. 6), corresponding to its higher me­
chanical properties (Fig. 8). Besides, due to the more precise layer
dimension control with higher layer numbering, the crystal sizes
detected from DSC and XRD showed a consistent trend, namely, a
decrease of crystal size (Table 1) and a higher packing factor (Fig. 7).
The good dispersion quality and higher nanotube orientations in the 64-
layered structures displayed the best mechanical properties (e.g.,
modulus, strength, E30% strain) (Fig. 8).
5. Conclusions
In summary, we have successfully built an MDIW 3D printing plat­
form and demonstrated its printability. We used the feedstock of PVA/
DMSO solutions and MWNTs/PVA/DMSO suspensions as an example to
fabricate multiphased and multilayered composites. The critical in
forming distinct microlayers was the viscosity matching between the
feedstock materials. The 64-layered composites showed much better
mechanical parameters (i.e., modulus, strength, and E30% strain) than any
other composites and the pure PVA due to thin layer thickness, more
interactive interfaces, preferential nanotube alignment, and improved
crystallization behavior. The dependence of properties on the multi­
layered composites and varying layer thickness suggested a new design
and manufacturing protocol. Our MDIW printing platform also demon­
strated a new 3D printing mechanism for layered structures and showed
high potential in surface patterning, layered laminates, circular scaf­
folds, and other functionally graded structures.
CRediT authorship contribution statement
Dharneedar Ravichandran: Conceptualization, Methodology,
Software, Verification, Formula analysis, Investigation, Data curation,
Writing – original draft, Writing – review & editing, Visualization.
Weiheng Xu: Methodology, Software, Validation, Formula analysis,
Investigation, Data curation, Writing – review & editing, Mounkia
Kakarla: Software, Validation, Data Curation, Writing – review &
editing. Sayli Jambulkar: Methodology, Validation, Investigation,
Writing – review & editing. Yuxiang Zhu: Validation, Writing – review
& editing. Kenan Song: Conceptualization, Writing – original draft,
D. Ravichandran et al. Additive Manufacturing 47 (2021) 102322

Writing – review & editing, Resources, Visualization, Supervision, [19] I. Blanco, The use of composite materials in 3D printing, J. Compos. Sci. 4 (2020)
42, https://doi.org/10.3390/jcs4020042.
Project administration.
[20] A. Arteiro, C. Furtado, G. Catalanotti, P. Linde, P.P. Camanho, Thin-ply polymer
composite materials: a review, Compos. Part A: Appl. Sci. Manuf. 132 (2020),
105777, https://doi.org/10.1016/j.compositesa.2020.105777.
Declaration of Competing Interest [21] B. Xue, L. Xie, Y. Bao, J. Zhang, Multilayered epoxy/glass fiber felt composites with
excellently acoustical and thermal insulation properties, J. Appl. Polym. Sci. 136
(2019) 1–7, https://doi.org/10.1002/app.46935.
The authors declare that they have no known competing financial [22] E. Baer, L. Zhu, 50th anniversary perspective: dielectric phenomena in polymers
interests or personal relationships that could have appeared to influence and multilayered dielectric films, Macromolecules 50 (2017) 2239–2256, https://
doi.org/10.1021/acs.macromol.6b02669.
the work reported in this paper.
[23] S. Ji, K. Yin, M. Mackey, A. Brister, M. Ponting, E. Baer, Polymeric nanolayered
gradient refractive index lenses: technology review and introduction of spherical
Appendix A. Supporting information gradient refractive index ball lenses, Opt. Eng. 52 (2013), 112105, https://doi.org/
10.1117/1.oe.52.11.112105.
[24] S.M. Bittner, J.L. Guo, A. Melchiorri, A.G. Mikos, Three-dimensional printing of
Supplementary data associated with this article can be found in the multilayered tissue engineering scaffolds, Mater. Today 21 (2018) 861–874,
online version at doi:10.1016/j.addma.2021.102322. https://doi.org/10.1016/j.mattod.2018.02.006.
[25] C. Aulin, E. Karabulut, A. Tran, L. Waìšgberg, T. Lindström, Transparent
nanocellulosic multilayer thin films on polylactic acid with tunable gas barrier
References properties, ACS Appl. Mater. Interfaces 5 (2013) 7352–7359, https://doi.org/
10.1021/am401700n.
[26] A. Li, X. Liao, H. Zhang, L. Shi, P. Wang, Q. Cheng, J. Borovilas, Z. Li, W. Huang,
[1] M. Attaran, The rise of 3-D printing: the advantages of additive manufacturing over
Z. Fu, M. Dontigny, K. Zaghib, K. Myers, X. Chuan, X. Chen, Y. Yang, Nacre-
traditional manufacturing, Bus. Horiz. 60 (2017) 677–688, https://doi.org/
inspired composite electrolytes for load-bearing solid-state lithium-metal batteries,
10.1016/j.bushor.2017.05.011.
Adv. Mater. 32 (2020) 1–9, https://doi.org/10.1002/adma.201905517.
[2] W. Xu, S. Jambhulkar, Y. Zhu, D. Ravichandran, M. Kakarla, B. Vernon, D.G. Lott,
[27] S. Ebnesajjad, Plastic films in food packaging materials, Technol. Appl. (2013).
J.L. Cornella, O. Shefi, G. Miquelard-Garnier, Y. Yang, K. Song, 3D printing for
[28] Z. Li, A. Olah, E. Baer, Micro- and nano-layered processing of new polymeric
polymer/particle-based processing: a review, Compos. Part B: Eng. 223 (2021),
systems, Prog. Polym. Sci. 102 (2020), 101210, https://doi.org/10.1016/j.
109102, https://doi.org/10.1016/j.compositesb.2021.109102.
progpolymsci.2020.101210.
[3] Y.Y.C. Choong, H.W. Tan, D.C. Patel, W.T.N. Choong, C.H. Chen, H.Y. Low, M.
[29] F. Ceccanti, E. Dini, X. De Kestelier, V. Colla, L. Pambaguian, 3D printing
J. Tan, C.D. Patel, C.K. Chua, The global rise of 3D printing during the COVID-19
technology for a moon outpost exploiting lunar soil, 61st Int. Astronaut. Congr.
pandemic, Nat. Rev. Mater. 5 (2020) 637–639, https://doi.org/10.1038/s41578-
2010, IAC 2010 11 (2010) 8812–8820.
020-00234-3.
[30] S. AL-Hasni, G. Santori, 3D printing of vacuum and pressure tight polymer vessels
[4] B.N.D. Rao, J.L. Olajide, R. Sadiku, 3D Print. Fiber Reinf. Polym. Nanocomposites:
for thermally driven chillers and heat pumps, Vacuum 171 (2020), 109017,
Addit. 3D Print. Fiber Reinf. Polym. Nanocomposites: Addit. Manuf. (2020),
https://doi.org/10.1016/j.vacuum.2019.109017.
https://doi.org/10.1007/978-3-030-11155-7.
[31] L. Van Dijk, E.A.P. Marcus, A.J. Oostra, R.E.I. Schropp, M. Di Vece, 3D-printed
[5] X. Wang, M. Jiang, Z. Zhou, J. Gou, D. Hui, 3D printing of polymer matrix
concentrator arrays for external light trapping on thin film solar cells, Sol. Energy
composites: a review and prospective, Compos. Part B Eng. 110 (2017) 442–458,
Mater. Sol. Cells 139 (2015) 19–26, https://doi.org/10.1016/j.
https://doi.org/10.1016/j.compositesb.2016.11.034.
solmat.2015.03.002.
[6] W. Xu, S. Jambhulkar, D. Ravichandran, Y. Zhu, M. Kakarla, Q. Nian, B. Azeredo,
[32] M. Mao, J. He, X. Li, B. Zhang, Q. Lei, Y. Liu, D. Li, The emerging frontiers and
X. Chen, K. Jin, B. Vernon, D.G. Lott, J.L. Cornella, O. Shefi, G. Miquelard-Garnier,
applications of high-resolution 3D printing, Micromachines 8 (2017) 1–20, https://
Y. Yang, K. Song, 3D printing-enabled nanoparticle alignment: a review of
doi.org/10.3390/mi8040113.
mechanisms and applications, Small 2100817 (2021), 2100817, https://doi.org/
[33] W.J. Schrenk, T. Alfrey, Coextruded multilayer polymer films and sheets, Polym.
10.1002/smll.202100817.
Blends. (1978) 129–165, https://doi.org/10.1016/b978-0-12-546802-2.50011-7.
[7] J.A. Lewis, J.E. Smay, J. Stuecker, J. Cesarano, Direct ink writing of three-
[34] P.A.G.S. Giachini, S.S. Gupta, W. Wang, D. Wood, M. Yunusa, E. Baharlou, M. Sitti,
dimensional ceramic structures, J. Am. Ceram. Soc. 89 (2006) 3599–3609, https://
A. Menges, Additive manufacturing of cellulose-based materials with continuous,
doi.org/10.1111/j.1551-2916.2006.01382.x.
multidirectional stiffness gradients, Sci. Adv. 6 (2020) 1–12, https://doi.org/
[8] B.G. Compton, J.A. Lewis, 3D-printing of lightweight cellular composites, Adv.
10.1126/sciadv.aay0929.
Mater. 26 (2014) 5930–5935, https://doi.org/10.1002/adma.201401804.
[35] Y. Liu, K. Li, M.M. Mohideen, S. Ramakrishna, Chapter 7 - Dissipative particle
[9] T. Chen, A. Sun, C. Chu, H. Wu, J. Wang, J. Wang, Z. Li, J. Guo, G. Xu, Rheological
dynamics simulations of centrifugal melt electrospinning, in: Y. Liu, K. Li, M.
behavior of titania ink and mechanical properties of titania ceramic structures by
M. Mohideen, S. Ramakrishna (Eds.), Melt Electrospinning, Academic Press, 2019,
3D direct ink writing using high solid loading titania ceramic ink, J. Alloy. Compd.
pp. 145–158, https://doi.org/10.1016/B978-0-12-816220-0.00007-5.
783 (2019) 321–328, https://doi.org/10.1016/j.jallcom.2018.12.334.
[36] C. Creton, P. Fabre, Chapter 14 - Tack, in: D.A. Dillard, A.V. Pocius, M. Chaudhury
[10] V.C.F. Li, C.K. Dunn, Z. Zhang, Y. Deng, H.J. Qi, Direct ink write (DIW) 3D printed
(Eds.), Adhes. Sci. Eng., Elsevier Science B.V, Amsterdam, 2002, pp. 535–575,
cellulose nanocrystal aerogel structures, Sci. Rep. 7 (2017) 1–8, https://doi.org/
https://doi.org/10.1016/B978-0-444-51140-9.50041-X.
10.1038/s41598-017-07771-y.
[37] B.S. Chee, G.G. de Lima, D. Devine, M.J.D. Nugent, 2 - Electrospun hydrogels
[11] C.M. Larson, J.J. Choi, P.A. Gallardo, S.W. Henderson, M.D. Niemack,
composites for bone tissue engineering, in: Inamuddin, A.M. Asiri, A. Mohammad
G. Rajagopalan, R.F. Shepherd, Direct ink writing of silicon carbide for microwave
(Eds.), Appl. Nanocomposite Mater. Orthop., Woodhead Publishing, 2019,
optics, Adv. Eng. Mater. 18 (2016) 39–45, https://doi.org/10.1002/
pp. 39–70, https://doi.org/10.1016/B978-0-12-813740-6.00003-X.
adem.201500298.
[38] W. Xu, D. Ravichandran, S. Jambhulkar, Y. Zhu, K. Song, Hierarchically structured
[12] J.W. Boley, K. Chaudhary, T.J. Ober, M. Khorasaninejad, W.T. Chen, E. Hanson,
composite fibers for real nanoscale manipulation of carbon nanotubes, Adv. Funct.
A. Kulkarni, J. Oh, J. Kim, L.K. Aagesen, A.Y. Zhu, F. Capasso, K. Thornton, P.
Mater. 2009311 (2021) 1–11, https://doi.org/10.1002/adfm.202009311.
V. Braun, J.A. Lewis, High-operating-temperature direct ink writing of mesoscale
[39] A.M. Jordan, B. Lee, K. Kim, E. Ludtke, O. Lhost, S.A. Jaffer, F.S. Bates, C.
eutectic architectures, Adv. Mater. 29 (2017), https://doi.org/10.1002/
W. Macosko, Rheology of polymer multilayers: slip in shear, hardening in
adma.201604778.
extension, J. Rheol. 63 (2019) 751–761, https://doi.org/10.1122/1.5109788.
[13] S. Chandrasekaran, B. Yao, T. Liu, W. Xiao, Y. Song, F. Qian, C. Zhu, E.B. Duoss, C.
[40] J. Han, H. Zhang, P. Chu, A. Imani, Z. Zhang, Friction and wear of high electrical
M. Spadaccini, Y. Li, M.A. Worsley, Direct ink writing of organic and carbon
conductive carbon nanotube buckypaper / epoxy composites, Compos. Sci.
aerogels, Mater. Horiz. 5 (2018) 1166–1175, https://doi.org/10.1039/
Technol. 114 (2015) 1–10, https://doi.org/10.1016/j.compscitech.2015.03.012.
c8mh00603b.
[41] R.M. Kumar, S. Kumar, B.V.M. Kumar, D. Lahiri, Effects of carbon nanotube aspect
[14] K. Chen, X. Kuang, V. Li, G. Kang, H.J. Qi, Fabrication of tough epoxy with shape
ratio on strengthening and tribological behavior of ultra high molecular weight
memory effects by UV-assisted direct-ink write printing, Soft Matter. 14 (2018)
polyethylene composite, Compos. PART A. 76 (2015) 62–72, https://doi.org/
1879–1886, https://doi.org/10.1039/c7sm02362f.
10.1016/j.compositesa.2015.05.007.
[15] M.A. Skylar-Scott, S. Gunasekaran, J.A. Lewis, Laser-assisted direct ink writing of
[42] A. Golchin, A. Wikner, N. Emami, An investigation into tribological behaviour of
planar and 3D metal architectures, Proc. Natl. Acad. Sci. USA 113 (2016)
multi-walled carbon nanotube / graphene oxide reinforced UHMWPE in water
6137–6142, https://doi.org/10.1073/pnas.1525131113.
lubricated contacts, Tribiol. Int. 95 (2016) 156–161, https://doi.org/10.1016/j.
[16] X. Wan, L. Luo, Y. Liu, J. Leng, Direct ink writing based 4D printing of materials
triboint.2015.11.023.
and their applications, Adv. Sci. 7 (2020) 1–29, https://doi.org/10.1002/
[43] C. Xu, B. Quinn, L.L. Lebel, D. Therriault, G. L’espérance, Multi-material direct ink
advs.202001000.
writing (DIW) for complex 3D metallic structures with removable supports, ACS
[17] H. Chen, X. Wang, F. Xue, Y. Huang, K. Zhou, D. Zhang, 3D printing of SiC ceramic:
Appl. Mater. Interfaces 11 (2019) 8499–8506, https://doi.org/10.1021/
direct ink writing with a solution of preceramic polymers, J. Eur. Ceram. Soc. 38
acsami.8b19986.
(2018) 5294–5300, https://doi.org/10.1016/j.jeurceramsoc.2018.08.009.
[44] S.R. Ahmad, R.J. Young, I.A. Kinloch, Raman spectra and mechanical properties of
[18] Y. Chen, P. Han, L. Vandi, A. Dehghan-manshadi, J. Humphry, D. Kent, I. Stefani,
graphene/polypropylene nanocomposites, Int. J. Chem. Eng. Appl. 6 (2015) 1–5,
P. Lee, M. Heitzmann, J. Cooper-white, M. Dargusch, A biocompatible thermoset
https://doi.org/10.7763/ijcea.2015.v6.440.
polymer binder for direct ink writing of porous titanium sca ff olds for bone tissue
[45] Z. Li, R.J. Young, I.A. Kinloch, N.R. Wilson, A.J. Marsden, A.P.A. Raju, Quantitative
engineering, Mater. Sci. Eng. C. 95 (2019) 160–165, https://doi.org/10.1016/j.
determination of the spatial orientation of graphene by polarized Raman
msec.2018.10.033.

13
D. Ravichandran et al.
spectroscopy, Carbon 88 (2015) 215–224, https://doi.org/10.1016/j.
carbon.2015.02.072.
[46] T. Liu, S. Kumar, Quantitative characterization of SWNT orientation by polarized
Raman spectroscopy, Chem. Phys. Lett. 378 (2003) 257–262, https://doi.org/
10.1016/S0009-2614(03)01287-9.
[47] H. Ajiki, T. Ando, Aharonov-Bohm effect in carbon nanotubes, Phys. B Phys.
Condens. Matter. 201 (1994) 349–352, https://doi.org/10.1016/0921-4526(94)
91112-6.
[48] X. Yang, M. Yao, W. Lu, S. Chen, M. Du, L. Zhu, H. Li, R. Liu, T. Cui, B. Sundqvist,
B. Liu, Polarized Raman study of aligned multiwalled carbon nanotubes arrays
under high pressure, J. Phys. Chem. C. 119 (2015) 27759–27767, https://doi.org/
10.1021/acs.jpcc.5b08161.
[49] G.L. Goh, S. Agarwala, W.Y. Yeong, Directed and on-demand alignment of carbon
nanotube: a review toward 3D printing of electronics, Adv. Mater. Interfaces 6
(2019), 1801318, https://doi.org/10.1002/admi.201801318.
[50] Y. Lee, R.S. Poter, Double-melting behavior of poly ( ether ether ketone),
Macromolecules 20 (1987) 1336–1341, https://doi.org/10.1021/ma00172a028.
[51] D.J. Blundell, On the interpretation of multiple melting peaks in poly(ether ether
ketone), Polymer 28 (1987) 2248–2251, https://doi.org/10.1016/0032-3861(87)
90382-X.
[52] M. Ren, F.H. Frimmel, G. Abbt-braun, Multi-cycle photocatalytic degradation of
bezafibrate by a cast polyvinyl alcohol / titanium dioxide ( PVA / TiO 2) hybrid
film, J. Mol. Catal. A, Chem. 400 (2015) 42–48, https://doi.org/10.1016/j.
molcata.2015.02.004.
[53] R.L. Blaine, Determination of polyethylene crystallinity by DSC, China Plast. 2002
(2002) 1–3. 〈http://www.tainstruments.com/pdf/literature/TA123new.pdf?fbclid
=IwAR3SmI9_boX-6EEdOaulhKfI2goyspND2rPJ6uBCMxhFwAM2ITHWYVXW
XEQ〉.
[54] Y. Kong, J.N. Hay, The enthalpy of fusion and degree of crystallinity of polymers as
measured by DSC, Eur. Polym. J. 39 (2003) 1721–1727, https://doi.org/10.1016/
S0014-3057(03)00054-5.
[55] Y. Kong, J.N. Hay, The measurement of the crystallinity of polymers by DSC,
Polymer 43 (2002) 3873–3878, https://doi.org/10.1016/S0032-3861(02)00235-
5.
[56] R.L. Blaine, Polymer Heats of Fusion, TA Instruments. (9999) 1–2.
[57] B. Wunderlich, Thermal Analysis, Acad. Press, 1990, pp. 417–431, https://doi.org/
10.1016/b978-0-12-765605-2.50001-7.
[58] H. Zhou, G.L. Wilkes, Comparison of lamellar thickness and its distribution
determined from d.s.c., SAXS, TEM and AFM for high-density polyethylene films
having a stacked lamellar morphology, Polymer 38 (1997) 5735–5747, https://doi.
org/10.1016/S0032-3861(97)00145-6.
[59] L. Lu, R.G. Alamo, L. Mandelkern, Lamellar thickness distribution in linear
polyethylene and ethylene copolymers, Macromolecules 27 (1994) 6571–6576,
https://doi.org/10.1021/ma00100a048.
[60] N. Alberola, J.Y. Cavaille, J. Perez, Mechanical spectrometry of alpha relaxations of
high-density polyethylene, J. Polym. Sci. Part B Polym. Phys. 28 (1990) 569–586,
https://doi.org/10.1002/polb.1990.090280410.
[61] O. Probst, E.M. Moore, D.E. Resasco, B.P. Grady, Nucleation of polyvinyl alcohol
crystallization by single-walled carbon nanotubes, Polymer 45 (2004) 4437–4443,
https://doi.org/10.1016/j.polymer.2004.04.031.
[62] R. Endo, S. Amiya, M. Hikosaka, Conditions for melt crystallization without
thermal degradation and equilibrium melting temperature of atactic poly(vinyl
alcohol), J. Macromol. Sci. - Phys. 42 B (2003) 793–820, https://doi.org/10.1081/
mb-120021607.
[63] J. Brandrup, E.H. Immergut, E.A.G. E. Polymer Handbook, Fourth ed.,, Wiley
Interscience Publicatiion, 1999.
[64] P.J. Peppas, N.A. Hansen, Crystallization kinetics of poly (vinyl Alcohol), J. Appl.
Polym. Sci. 27 (1982) 4787–4797, https://doi.org/10.1002/app.1982.070271223.
[65] K. Song, Y. Zhang, J. Meng, M.L. Minus, Lubrication of poly(vinyl alcohol) chain
orientation by carbon nano-chips in composite tapes, J. Appl. Polym. Sci. 127
(2013) 2977–2982, https://doi.org/10.1002/app.37963.
[66] D. Richard, T. Speck, The role of shear in crystallization kinetics: From suppression
to enhancement, Sci. Rep. 5 (2015) 1–7, https://doi.org/10.1038/srep14610.
[67] J.J. Cerdà, T. Sintes, C. Holm, C.M. Sorensen, A. Chakrabarti, Shear effects on
crystal nucleation in colloidal suspensions, Phys. Rev. E - Stat. Nonlinear, Soft
Matter. Phys. 78 (2008) 1–16, https://doi.org/10.1103/PhysRevE.78.031403.
[68] A.K. Patel, R. Bajpai, J.M. Keller, On the crystallinity of PVA/palm leaf
biocomposite using DSC and XRD techniques, Microsyst. Technol. 20 (2014)
41–49, https://doi.org/10.1007/s00542-013-1882-0.
[69] P.K. Dubey, R. Bajpai, J.M. Keller, Structural, morphological and microhardness
characterization in polymer complex of laser dye rhodamine (Rh6G) doped
polymethyl methacrylate, Microsyst. Technol. 14 (2008) 1165–1171, https://doi.
org/10.1007/s00542-008-0650-z.
[70] B.G. Colvin, Crystal structure of polyvinyl alcohol, Nature 248 (1974) 756–759,
https://doi.org/10.1038/248756a0.
[71] S. Dabhi, P.K. Jha, Structural and electronic properties of poly(vinyl alcohol) using
density functional theory, AIP Conf. Proc. 1591 (2014) 1133–1134, https://doi.
org/10.1063/1.4872878.
14
Additive Manufacturing 47 (2021) 102322
[72] G. Landon, G. Lewis, G.F. Boden, The influence of particle size on the tensile
strength of particulate - filled polymers, J. Mater. Sci. 12 (1977) 1605–1613,
https://doi.org/10.1007/BF00542811.
[73] A. Martone, C. Formicola, M. Giordano, M. Zarrelli, Reinforcement efficiency of
multi-walled carbon nanotube/epoxy nano composites, Compos. Sci. Technol. 70
(2010) 1154–1160, https://doi.org/10.1016/j.compscitech.2010.03.001.
[74] S.V. Harb, S.H. Pulcinelli, C.V. Santilli, K.M. Knowles, P. Hammer, A comparative
study on graphene oxide and carbon nanotube reinforcement of PMMA-siloxane-
silica anticorrosive coatings, ACS Appl. Mater. Interfaces 8 (2016) 16339–16350,
https://doi.org/10.1021/acsami.6b04780.
[75] A. Martone, G. Faiella, V. Antonucci, M. Giordano, M. Zarrelli, The effect of the
aspect ratio of carbon nanotubes on their effective reinforcement modulus in an
epoxy matrix, Compos. Sci. Technol. 71 (2011) 1117–1123, https://doi.org/
10.1016/j.compscitech.2011.04.002.
[76] V. Panwar, K. Pal, Dynamic Mechanical Analysis of Clay-Polymer Nanocomposites,
Elsevier Inc, 2017, https://doi.org/10.1016/B978-0-323-46153-5.00012-4.
[77] M.F. Yu, O. Lourie, M.J. Dyer, K. Moloni, T.F. Kelly, R.S. Ruoff, Strength and
breaking mechanism of multiwalled carbon nanotubes under tensile load, Science
287 (80) (2000) 637–640, https://doi.org/10.1126/science.287.5453.637.
[78] R.O.R.B.G. Demczyk, Y.M. Wang, J. Cumings, M. Hetman, W. Han, A. Zettl, Direct
mechanical measurement of the tensile strength and elastic modulus of
multiwalled carbon nanotubes, Mater. Sci. Eng.: A 334 (2002) 173–178, https://
doi.org/10.1016/S0921-5093(01)01807-X.
[79] X. Li, G.B. Mckenna, G. Miquelard-Garnier, A. Guinault, C. Sollogoub, G. Regnier,
A. Rozanski, Forced assembly by multilayer coextrusion to create oriented
graphene reinforced polymer nanocomposites, Polymer 55 (2014) 248–257,
https://doi.org/10.1016/j.polymer.2013.11.025.
[80] Y. Bin, M. Mine, A. Koganemaru, X. Jiang, M. Matsuo, Morphology and mechanical
and electrical properties of oriented PVA-VGCF and PVA-MWNT composites,
Polymer 47 (2006) 1308–1317, https://doi.org/10.1016/j.polymer.2005.12.032.
[81] Y. Huang, Y. Zheng, W. Song, Y. Ma, J. Wu, L. Fan, Poly(vinyl pyrrolidone)
wrapped multi-walled carbon nanotube/poly(vinyl alcohol) composite hydrogels,
Compos. Part A Appl. Sci. Manuf. 42 (2011) 1398–1405, https://doi.org/10.1016/
j.compositesa.2011.06.003.
[82] J.A. Lewis, Direct ink writing of 3D functional materials, Adv. Funct. Mater. 16
(2006) 2193–2204, https://doi.org/10.1002/adfm.200600434.
[83] I. Gouzman, N. Atar, E. Grossman, R. Verker, A. Bolker, M. Pokrass, S. Sultan,
O. Sinwani, A. Wagner, T. Lück, C. Seifarth, 3D Printing of Bismaleimides: from
new ink formulation to printed thermosetting polymer objects, Adv. Mat. 1900368
(2019) 1–8, https://doi.org/10.1002/admt.201900368.
[84] L.R. Lopes, A.F. Silva, O.S. Carneiro, Multi-material 3D printing: the relevance of
materials affinity on the boundary interface performance, Addit. Manuf. 23 (2018)
45–52, https://doi.org/10.1016/j.addma.2018.06.027.
[85] C.S. O’Bryan, T. Bhattacharjee, S.R. Niemi, S. Balachandar, N. Baldwin, S.
T. Ellison, C.R. Taylor, W.G. Sawyer, T.E. Angelini, Three-dimensional printing
with sacrificial materials for soft matter manufacturing, MRS Bull. 42 (2017)
571–577, https://doi.org/10.1557/mrs.2017.167.
[86] H. Yuk, X. Zhao, A new 3D printing strategy by harnessing deformation, instability,
and fracture of viscoelastic inks, Adv. Mater. 30 (2018), 1704028, https://doi.org/
10.1002/adma.201704028.
[87] L. Li, Q. Lin, M. Tang, A.J.E. Duncan, C. Ke, Advanced polymer designs for direct-
ink-write 3D printing, Chem. - A Eur. J. 25 (2019) 10768–10781, https://doi.org/
10.1002/chem.201900975.
[88] B.M. Rauzan, A.Z. Nelson, S.E. Lehman, R.H. Ewoldt, R.G. Nuzzo, Particle-free
emulsions for 3D printing elastomers, Adv. Funct. Mater. 28 (2018) 1–12, https://
doi.org/10.1002/adfm.201707032.
[89] Q. Wang, J. Sun, Q. Yao, C. Ji, J. Liu, Q. Zhu, 3D printing with cellulose materials,
Cellulose 25 (2018) 4275–4301, https://doi.org/10.1007/s10570-018-1888-y.
[90] S. Srivastava, N.A. Kotov, Nanoparticle assembly for 1D and 2D ordered structures,
Soft Matter. 5 (2009) 1146–1156, https://doi.org/10.1039/b812115j.
[91] S.M. Doshi, E.T. Thostenson, Thin and flexible carbon nanotube-based pressure
sensors with ultrawide sensing range, ACS Sens. 3 (2018) 1276–1282, https://doi.
org/10.1021/acssensors.8b00378.
[92] A.O. Borode, N.A. Ahmed, P.A. Olubambi, A review of heat transfer application of
carbon-based nanofluid in heat exchangers, Nano-Struct. Nano-Objects 20 (2019),
100394, https://doi.org/10.1016/j.nanoso.2019.100394.
[93] D. Maiti, X. Tong, X. Mou, K. Yang, Carbon-based nanomaterials for biomedical
applications: a recent study, Front. Pharmacol. 9 (2019) 1–16, https://doi.org/
10.3389/fphar.2018.01401.
[94] S. Agnelli, S. Pandini, A. Serafini, S. Musto, M. Galimberti, Anisotropic nonlinear
mechanical behavior in carbon nanotubes/poly(1,4-cis-isoprene) nanocomposites,
Macromolecules 49 (2016) 8686–8696, https://doi.org/10.1021/acs.
macromol.6b01682.
[95] L. Deng, S.J. Eichhorn, C.C. Kao, R.J. Young, The effective young’s modulus of
carbon nanotubes in composites, ACS Appl. Mater. Interfaces 3 (2011) 433–440,
https://doi.org/10.1021/am1010145.