Journal of the European Ceramic Society 36 (2016) 3409–3415

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Journal of the European Ceramic Society

journal homepage: www.elsevier.com/locate/jeurceramsoc

Fabrication of ZnO periodic structures by 3D printing

Carmen R. Tubío, Francisco Guitián, Alvaro Gil ∗
Instituto de Cerámica, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain

a r t i c l e i n f o a b s t r a c t

Article history: In this study, aqueous colloidal ZnO inks with tailored rheological properties have been developed for 3D
Received 28 December 2015 printing of periodic structures. These periodic structures consisting of alternating layers with tetragonal
Received in revised form 13 May 2016 symmetries were fabricated by extrusion of ZnO inks with concentration of 48 vol%. The as-prepared
Accepted 15 May 2016
structures had well-defined and interconnected layers with rod diameters of 200 ␮m. The inks exhibited
Available online 28 May 2016
pseudoplastic behaviour and were in accordance with the power-law model. Oscillatory and creep-
recovery measurements indicated that the inks had the appropriate viscoelastic behaviour and excellent
Keywords:
printing characteristics. In order to acquire a high mechanical strength, the structures were sintered
3D Printing
ZnO
at various temperatures between 900 and 1500 ◦ C, and their compressive strength was evaluated. The
Ceramic ink results indicated that 1500 ◦ C was an optimum sintering temperature to obtain structures with high com-
Rheology pressive strength up to 11.09 MPa. The reported ZnO inks offer multiple possibilities for the fabrication
Sintering of novel structures for practical applications.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction
The design and fabrication of devices from the micro- to
mesoscale with high precision is of crucial importance for the future
advance of the technology fields such as electronics, optoelec-
tronics, photonics, energy, biotechnology and life sciences. Among
various semiconductors, zinc oxide (ZnO) is a very promising mate-
rial for multiple applications. ZnO is a wide bandgap semiconductor
(Eg = 3.37 eV at room temperature) that displays excellent physical
properties including piezoelectric, electrical, optical, thermal and
mechanical properties [1,2]. In addition, ZnO is biodegradable and
biocompatible for biomedical applications [3]. As a consequence, in
recent years the development of a wide variety of functional ZnO
devices has been seen, from solar cells, piezoelectrics, varistors and
sensors devices to optical such as light-emitting diodes and opti-
cally pumped lasers[4]. However, these and further applications
could be still limited by the fabrication methods, as there are criti-
cal issues such as the resolution and the geometry of the structures.
There are several methods to fabricate mesoscale ZnO structures,
such as sol-gel [5], epitaxial growth [6], stereolitography [7]. Within
this context, one promising technique that has attracted consider-
able attention, due to its simplicity and ability to fabricate complex
structures, is the three-dimensional (3D) printing [8]. 3D print-
ing is a highly versatile technique to fabricate complex structures
∗ Corresponding author.
E-mail address: alvaro.gil@usc.es (A. Gil).
with high precision and nanometer resolution. The principle of this
technique is based on the extrusion of continuous filaments (inks)
in a layer-by-layer sequence using computer-aided design (CAD)
tools. This method is capable of fabricating structures with feature
sizes on the microscale (0.1–100 ␮m) and mesoscale (>100 ␮m),
depending on the nozzle diameter. The ability to fabricate a variety
of structures requires a good control over the formulation and rhe-
ological behaviour of the inks and the printing parameters (velocity
printing, pressure extrusion). To date, a wide variety of materi-
als have been printed using colloidal [9], polymer hydrogels [10]
and metal nanoparticle [11] inks. The potential of this method was
demonstrated for different applications that including electronics
[12], biomaterials [13], catalysis [14], photonic bandgap materials
[15] and tissue engineering scaffolds [16].
The use of 3D printing for the production of structures in
the mesoscale, using high concentrated colloidal inks (typically
40–50 vol%) has been studied intensively during the last decade.
Various suspensions for 3D printing containing ceramic powders
such as SiO2 [9], SiC [17], BaTiO3 [18], ZrO2 [19], Al2 O3 [20] and
graphene oxide [21] have been explored. These colloidal inks need
to satisfy special requirements in order to be used in the 3D print-
ing process[8]. The ink must have a controlled viscoelastic response
with pseudoplastic (shear-thinning) to flow through nozzle, and
then retain its shape after printing. It must also have low viscos-
ity and high solid loading to minimize the drying which induce
shrinkage after printing, and possess good dispersion and stabil-
ity of ceramic powders to avoid sedimentation and the clogging
of the nozzles. These characteristics can be managed by control-

http://dx.doi.org/10.1016/j.jeurceramsoc.2016.05.025
0955-2219/© 2016 Elsevier Ltd. All rights reserved.
3410 C.R. Tubío et al. / Journal of the European Ceramic Society 36 (2016) 3409–3415

Fig. 1. Experimental set-up for the robotic deposition apparatus used for the fabrication of the ZnO periodic structures.

ling factors such as the particle size distribution of the ceramic

powders, and solid loading and composition of the ink. In order to
formulate stable aqueous colloidal suspension with high solid load-
ing, it is necessary to disperse the particles in an aqueous medium
adjusting the pH or via electrostatic or steric stabilization. The well-
dispersed colloidal suspension is then gelled by adjusting the pH
to the isoelectric point, adding specific concentrations of salt or by
a bridging flocculation with a polyelectrolyte, where the particles
form an interconnected network with the medium [22,18].
This study was focused on preparing printable aqueous colloidal
ZnO ink with the required rheological behaviour to fabricate peri-
odic structures by 3D printing. First, we evaluate the effectiveness
of two polyelectrolytes as dispersant and gelificant for the ZnO
powders by a sedimentation test. Then, we verified that ZnO ink
is suitable for printing by rheological experiments that including
steady-state, oscillatory and creep-recovery measurements. Fur-
ther, to demonstrate the viability for printing of the ink, we create
periodic lattices using a 200 ␮m nozzle. Finally, different thermal
treatments were performed to burnout the polymers, reduce the
porosity of the structure and provide mechanical strength to the
material.

2. Experimental

2.1. Materials

ZnO powder (Sigma-Aldrich) with an average particle size of

0.7 ␮m (estimated by Sedigraph 5100, Micromeritics Inc., USA) was
used. The powder was dispersed in deionized water with a disper-
sant ammonium salt of poly(acrylic acid)(PAA) (Darvan 821A, R.T.
Vanderbilt Company Inc., USA). The polymer binders used included
a viscosifier agent (hydroxypropyl methylcellulose, HPMC, Sigma-
Aldrich) and a gelation agent poly(ethylenimine, PEI, MW = 2000,
Sigma-Aldrich). Table 1 summarises the main physicochemical
characteristics of the ink components.
Fig. 2. (a) X-ray diffraction patterns of as-received and calcined at 1500 ◦ C ZnO
2.2. Determination of the optimum concentrations of dispersant powders. (b) SEM image of as-received ZnO powders.
and flocculant

aqueous ZnO suspensions (5 vol%) with the optimized dispersant

The optimum concentrations of the dispersant and flocculant
concentration and with different flocculant concentration (0.1, 0.2
in the ink was studied by sedimentation measurements. Aqueous
and 0.3 wt% based on powder) were prepared by the same proce-
ZnO suspensions (5 vol%) with different dispersant concentrations
dure described above.
(0.5, 1, 1.5 and 2 wt% based on powder) were prepared. These sus-
pensions were performed for 15 min in an ultrasonic probe (U200S,
IKA Labortechnik, Germany). Then, 10 mL (H0 ) of each suspension 2.3. Ink synthesis
were placed in different graduated cylinder tubes to measure after
24 h the sediment height (Ht ) as function of the dispersant concen- The preparation of ZnO inks with concentrations of 44, 46, 48,
tration. To evaluate the optimum concentration of the flocculant, 50 and 52 vol% followed a three-step procedure. To formulate these
 C.R. Tubío et al. / Journal of the European Ceramic Society 36 (2016) 3409–3415 3411

Table 1
Physicochemical characteristics of the ZnO ink components.

Component Function Character Density (g/mL) at 25 ◦ C Viscosity (Pa s) at 20 ◦ C

ZnO Filler Amphoteric 5.89 –

Darvan 821A Dispersant Anionic 1.25 0.03–0.05
HPMC Viscosifier Nonionic 1.26–1.31 4
PEI Gelation Cationic 1.08 0.5–0.9

inks, 126.2 g of ZnO powder (30 vol%) was first dispersed in a 50 mL

of an aqueous suspension containing Darvan 821A (2 wt%, based on
powder). This suspension was performed for 15 min in the ultra-
sonic probe, and then centrifuged at 2500 rpm for 15 min. To follow,
and depending on the final concentration desired, a known volume
of supernatant was removed. The suspension was then mixed for
2 min at 2000 rpm using a mixer Thinky ARE-250 (Thinky, USA).
To increase the viscosity of the ink, the HPMC was added at a con-
centration of 0.074 wt% (based on powder), and stored for 1 h to
get a hydration and polymer chain relaxation. Finally, the ink was
gelified by adding 0.1 wt% (based on powder) of the flocculant PEI.
ZnO ink was again mixed several times at 2000 rpm for 3 min until
optimum homogenization.

2.4. Rheological characterization

The rheological properties of the inks were measured using

a rotational rheometer Kinexus Pro (Malvern Instruments Ltd.,
UK) fitted with a parallel plate geometry (plate diameter = 20 mm,
gap = 1 mm). The measurements were carried out at 25 ◦ C using a
solvent trap filled with deionized water to minimize the evapora-
tion of the ink. In all studies, the samples were pre-sheared at 1 s−1
for 2 min before each measurement, followed by a 10 min equilib-
rium time to minimize the effect of the ink loading. A steady-state
test for the ZnO ink (44–52 vol%) was obtained varying the shear
rate between 0 and 80 s−1 . A stress sweep test was conducted from
0 to 100 Pa at a constant frequency of 1 Hz to determine the linear
viscoelastic region (LVR). A frequency sweep test was conducted in
a frequency range of 0.1–10 Hz at a constant stress selected form
LVR ( = 8 Pa). After the frequency sweep, the ink was allowed for
10 min followed by a creep-recovery measurement. In the creep
experiment, a constant shear stress selected within LVR ( = 8 Pa)
was applied for 60 s and the resulting strain was measured. Then,
in the recovery test, the stress was removed and the strain was
recorded for another 180 s. This study was made in the absence of Fig. 3. The relative sedimentation height for ZnO suspensions (5 vol%) as a function
the solvent trap. of: (a) dispersant concentration, (b) flocculant concentration at 2 wt% of dispersant
Darvan 821A.

2.5. Printing experiments 2.6. Microstructure characterization

In order to evaluate the printing of the ZnO ink, periodic struc-
tures of various geometries were fabricated using the robotic
deposition apparatus shown in Fig. 1 (A3200, Aerotech Inc., USA),
which motion was controlled by computer aided design (CAD) soft-
ware Robocad 3.4 (3D Inks, USA). CAD data are transformed into
g-codes to control the motion of the robotic device. The system
was equipped with an air powered fluid dispenser Performus VII
attached to HP7x (Nordson EFD, USA) to control the ink flow rate.
The ink was housed in a syringe (3 mL, Nordson EFD, USA) attached
by a nozzle with diameter 200 ␮m (Nordson EFD, USA). An adequate
pressure is applied to the dispensing nozzle during the printing
process. After printing, the periodic structures were dried under
ambient conditions for 24 h. Then, they were sintered at tempera-
tures of 900, 1100, 1300 and 1500 ◦ C for 2.5 h in air with a heating
rate of 5 ◦ C/min.
The phase composition of the ZnO powders were analysed by X-
ray diffractometer Siemens D5000 (Siemens, Germany) with Cu K␣
radiation. The data was collected in the 2␪ range from 20 to 60◦ , in
steps of 0.05◦ . The specific surface area of the powders was analysed
using the N2 gas adsorption (Gemini 2360 V2.01, Micromeritics
Inc., USA). The real density of the powder was determined using
a helium pycnometer (Accupyc 1330, Micromeritics Inc., USA). The
dried structures were examined in a stereomicroscope Olympus
SZX12 (Olympus, Japan). The surface morphology of the commer-
cial powders and the sintered structures was observed by scanning
electron microscopy (SEM) (JEOL 6400, JEOL Corporation, Japan).
The compressive strength of the sintered structures was tested
using a Suzpecar universal testing machine with a constant load-
ing rate of 0.5 mm/min. The test was performed on cylindrical ZnO
printed structures with 8 mm of diameter and 10 mm of height.
3412 C.R. Tubío et al. / Journal of the European Ceramic Society 36 (2016) 3409–3415

Fig. 5. (a) Stress sweep test at 1 Hz for ZnO ink. (b) Frequency sweep test for ZnO
ink in the LVR region.

Fig. 4. (a) Viscosity curves of ZnO inks at various solid loading and the corresponding
fitting curves for the power-law model. (b) Relative viscosity dependence on the
solid loading at a shear rate of 40 s−1 . The solid line represents the Krieger-Dougherty
model fitted.

3. Results and discussion

3.1. Characterization of the ZnO ceramic powder

The XRD pattern of the ZnO powders as-received and calcined

at 1500 ◦ C indicated the presence of the wurtzite phase (JCPDS card
No. 89-0511) without any additional diffraction peaks (Fig. 2a). The
SEM image in Fig. 2b revealed that the as-received powders have an
irregular shape. The particle size of the powders determined from
the SEM images was in the range from 0.3 to 0.6 ␮m. This value
correlated well with the particle size determinate by Sedigraph
analysis (average particle size of 0.7 ␮m). The powder exhibited
a density of 5.89 g/mL and a specific surface area of 5.25 m2 /g.

3.2. Optimization of the ZnO ink

The state of dispersion and gelation of the ZnO suspensions were
evaluated by a sedimentation test in terms of the relative sedi-
mentation height, which considered the ratio of the height of the
sediment (Ht ) to the initial height (H0 ) of the total suspension as a
function of settling time. A colloidal stable suspension gives high
values for the relative sedimentation height, while a flocculated
Fig. 6. Creep-recovery behaviour of the ZnO ink with a solid loading of 48 vol%. Solid
line represents adjustment to the Burger model.
suspension gives low values. Fig. 3a shows the relative sedimenta-
tion height of the ZnO suspensions as a function of the dispersant
Darvan 821A (electrosteric dispersant). The fastest setting rate was
observed for the suspension without any addition of dispersant.
 C.R. Tubío et al. / Journal of the European Ceramic Society 36 (2016) 3409–3415 3413

Fig. 7. Optical images of the dried ZnO structures with: (a) cylindrical lattice with st symmetry (10 layers, 200 ␮m rod spacing), (b) square lattice with fct symmetry (20
layers, 566 ␮m rod spacing). Cross-sectional SEM images of the ZnO periodic structures with fct symmetry sintered at different temperatures: (c) 900 ◦ C and (d) 1500 ◦ C.

Fig. 8. SEM images of the surface of the ZnO structure sintered at different temperatures: (a) 900 ◦ C, (b) 1100 ◦ C, (c) 1300 ◦ C, (d) 1500 ◦ C.

From the figure, it is clear that the suspension containing 2 wt% of gelation of the suspension was induced by a bridging flocculation
Darvan 821A had the slowest sedimentation rate. Consequently, an with the flocculant PEI, which yields an interconnecting particle
addition of 2 wt% of dispersant will be the most effective in prevent- network (the positively charged amine groups of the flocculant PEI
ing the sedimentation of the ZnO powders. On the other hand, the create links with the negatively charged carboxylic acid groups of
3414 C.R. Tubío et al. / Journal of the European Ceramic Society 36 (2016) 3409–3415

max = 60.37 and n = 5.45. Below a ZnO concentration of 48 vol%, the

viscosity curve is flat, and in this range a change of concentration
does not results in a critical increase of the viscosity. However the
viscosity of the ink increased sharply above 48 vol%. Consequently,
the ZnO ink with a solid volume fraction of 48 vol% was chosen for
the experimental studies of printability.
To investigate the viscoelastic behaviour of the ZnO ink (48 vol%)
different oscillatory experiments were made. First, a stress sweep
test was conducted to identify the linear viscoelastic region for the
ZnO ink. The elastic G and viscous G modulus as a function of the
shear stress are shown in Fig. 5a. At low stress, G and G are con-
stant (linear region) until a critical stress value (yield stress) where
both modulus decrease. This value is around 11 Pa (G = 0.9 G eq )
and indicates the minimum stress that must be applied to initi-
ate a significant flow in the ink. In the linear region G > G , which
indicate that the ink is highly structured, with a plateau value of G
of 2 × 104 Pa. Previous studies have determined the minimum ink
elasticity to build a 3D periodic structure without deflections in the
rods [25]. Based on this calculation, a minimum G of 5.32 × 102 Pa
is required for the conditions given in this study (i.e., 3.024 g/mL
Fig. 9. Compressive strength of ZnO structures sintered at different temperatures.
ink density, 566 ␮m rod spacing and 200 ␮m rod diameter). Con-
sequently, the ZnO ink that exhibits a G of 2 × 104 Pa satisfies this
Table 2
Rheological parameters of the ZnO inks. criterion. In Fig. 5b a frequency sweep study in the linear region
is displayed, thus allowing identifying the internal structure of
40 (Pa s) K(Pa sn ) R2
Solid loading (vol%) n
the ink. It was observed that G > G , and both increased with the
44 0.05 1.1 0.33 0.89 increasing of the frequency. The profile of the phase angle ı (tan ı =
46 2.78 100.1 0.23 0.95 G / G ), which is an indicator of the elastic or viscous behaviour of
48 6.53 135.1 0.38 0.84
the ink, is also shown. When ı = 0◦ the material is perfectly elas-
50 14.96 402.8 0.27 0.94
52 47.82 879.4 0.18 0.92 tic (solid-like behaviour), ı = 90◦ is perfectly viscous (liquid-like
behaviour) and in the intermediate range of 0◦ < ı < 90◦ the suspen-
sion exhibit a viscoelastic behaviour (ı > 45◦ more viscous, ı < 45◦
the Darvan 821A that cover the ZnO particles). Fig. 2b shows the more elastic). In the ZnO ink, a phase angle smaller than 45◦ indicate
variation of the relative sedimentation height of the suspension the dominantly elastic behaviour.
(with a 2 wt% of dispersant Darvan 821A) as a function of the floc- The viscoelastic properties of the ZnO ink (48 vol%) before yield,
culant concentration. The optimum value of PEI was estimated to be was also measured by a creep-recovery test. In the creep test, the
0.1 wt%, because showed the lowest relative sedimentation height. ink was subjected to a constant shear stress (within the linear
Once the optimal dispersant and flocculant concentrations were range), and the corresponding strain was measured in function of
known, the effect of different solid loading (44–52 vol%) on the flow time. Then, in the recovery test, the applied stress was stopped
behaviour was studied. Fig. 4a shows this effect on the viscosities of and the strain was further measured for 180 s. Fig. 6 shows the
ZnO ink containing 2 wt% dispersant and 0.1 wt% flocculant. These experimental results of the compliance J(t) (ratio between the mea-
curves present the typical shape observed in fluids with pseudo- sured strain and the applied stress) as a function of the time for
plastic (shear-thinning) behaviour, where the apparent viscosity the ZnO ink (48 vol%). These results demonstrated that the ZnO ink
decreases with the increasing of the shear rate. This dependence present a viscoelastic behaviour, showing a considerable nonlin-
between the viscosity and the shear rate can be described by the ear growth in the creep test and exponential decay in the recovery
power-law model [23]: test [26]. The experimental data were satisfactorily fitted to the
Burger viscoelastic model (R2 = 0.95). This is a mechanical model
 = K ˙ n−1 (1)
with four parameters (a linear combination of Maxwell and Kelvin-
where  is the apparent viscosity, K is the consistency index, ˙ is Voight elements), which gives a good representation of the creep
the shear rate and n is the flow behaviour index. Table 2 summa- behaviour of viscoelastic materials [26]. The grade of recovery (R)
rizes the fitting parameters of the power-law model and the 40 of the ink, which is the ability to return from deformation, was
(viscosity at 40 s−1 shear rate). The values of the exponent 0 < n < 1 calculated as follows:
for all inks show clearly their pseudoplastic behaviour. In Fig. 4a Jmax − J∞
was observed that the apparent viscosity of the ink was strongly R= (3)
Jmax
dependent on the solid loading. The change in the viscosity with
different concentrations at a constant shear rate (40 s−1 , typically where Jmax and J∞ are the compliance at the end of the creep and the
shear rate printing) is shown in Fig. 4b. This dependence can be recovery test, respectively. Depending on the applied stress and its
correlated according to the modified Krieger-Dougherty equation duration, the recovery of viscoelastic materials may become total
[24]: or partial. The ZnO ink presented a partial recovery of 48.16%. This
 
−n result is in agreement with previous results using similar partic-
rel = 1− (2) ulate suspensions [27]. The creep-recovery result confirmed the
max frequency sweep test, demonstrating that ZnO ink was viscoelastic.
where rel is the relative viscosity (apparent viscosity divided by
the solvent viscosity),  and max are the apparent volume frac- 3.3. Printing and characterization of the 3D periodic structures
tion and the maximum volume fraction of solids in the suspension,
respectively, and n is the fitting parameter. This model provided a After the optimization of the ink composition, cylindrical and
satisfactory description (R2 = 0.99) for the ZnO inks with values of square lattices were printed with 200 ␮m diameter nozzle to
 C.R. Tubío et al. / Journal of the European Ceramic Society 36 (2016) 3409–3415
demonstrate the versatile designs achievable with the ZnO ink by
3D printing. Fig. 7a and b shows the surface of a dried cylindrical
lattice with simple-tetragonal (st) symmetry and a dried square
lattice consisting of alternating layers of parallel rods offset by
90◦ with face-centered-tetragonal (fct) symmetry. These periodic
structures were fabricated using a pressure of 14 bar and a veloc-
ity printing of 4 mm/s. These results clearly demonstrate that it
was possible to create uniform and well-shaped lattices, which is
indicative of the high quality of the ZnO ink (48 vol%) for the 3D
printing process. Fig. 7c–d shows the cross-section SEM images of
the ZnO structure with fct symmetry after sintering at 900 ◦ C and
1500 ◦ C for 2.5 h in air, respectively. The sintered structures exhib-
ited a homogeneous morphology, free of cracks and interconnected
porous structure without deformations. However, the rod volumet-
ric shrinkage increased from ∼25% to ∼28% when the temperature
increased from 900 to 1500 ◦ C.
Furthermore, strength ZnO structures for many potential appli-
cations are strongly required. To develop structures with a high
mechanical strength, we sintered them at different temperatures
in the range of 900–1500 ◦ C (Fig. 8). The results indicated that
the samples sintered between 900–1300 ◦ C (Fig. 8a–c) presented
grains of nanometric sizes, randomly distributed and irregularly
disoriented. But an increase in the sintering temperature at 1500 ◦ C
(Fig. 8d) resulted in a coalescence of the smaller grains with a little
increase in the grain size, and a decrease in macroporosity of the
ZnO structure.
The compressive mechanical properties of these sintered struc-
tures were evaluated using a uniaxial testing machine. Fig. 9 shows
the dependence of compressive strength with the sintering temper-
ature. As expected, the compressive strength changed from 5.08 to
11.09 MPa, with the increase of the sintering temperature from 900
to 1500 ◦ C.
4. Conclusions
Cylindrical and square periodic ZnO structures were fabricated
using 3D printing technique by optimizing the composition of the
ink, processing conditions and the sintering stage. Sedimentation
measurements allowed for the determination of the optimal con-
centrations of the dispersant (2 wt%) and flocculant (0.1 wt%) in the
ink. All prepared ZnO inks (44–52 vol%) exhibited a pseudoplastic
behaviour described by the power-law model. Specially, the ZnO
ink with solid loading of 48 vol% showed viscoelastic behaviour,
with adequate elastic modulus for the fabrication of self-supporting
structures. For this ink concentration, complex 3D periodic lat-
tice structures were printed by a 200 ␮m nozzle. The effect of
sintering temperature on the microstructure was evaluated, and
1500 ◦ C for 2.5 h produced structures with compressive strengths of
11.09 MPa. This approach will be a significant step towards the fab-
rication of 3D ZnO structures that will facilitate the development of
next-generation devices using ceramics components in numerous
practical applications.
Acknowledgements
Financial support from projects grants No. 10PXIB265118PRand
No. GPC2013/019 funded by the Government of Galicia (Spain) is
gratefully acknowledged.
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