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Received: 18 January 2021    Revised: 19 April 2021    Accepted: 19 April 2021

DOI: 10.1111/jace.17874

ORIGINAL ARTICLE

Three-­dimensional printing of zirconia scaffolds for load bearing

applications: Study of the optimal fabrication conditions

Anuraag Gaddam1   | Daniela S. Brazete1   | Ana S. Neto1   | Bo Nan1,2   |

José M. F. Ferreira1

1
Department of Materials and Ceramics
Engineering, CICECO, University of
Aveiro, Aveiro, Portugal
2
State Key Laboratory of Materials
Processing and Die & Mould Technology,
School of Materials Science and
Engineering, uazhong University of
Science and Technology, Wuhan, China
Correspondence
Anuraag Gaddam, Department of
Materials and Ceramics Engineering,
CICECO, University of Aveiro, Aveiro,
Portugal.
Email: anuraagg@ua.pt
Funding information
Fundação para a Ciência e a Tecnologia,
Grant/Award Number: UID/
CTM/50011/2019
Abstract
Yttria-­stabilized zirconia (YSZ) scaffolds with a planned macroporosity fraction of
about 70% were fabricated by Robocasting from inks with high solid loadings. The ef-
fects of solids loading and the concentrations of processing additives on the flow be-
havior of the starting suspensions and the viscoelastic properties of the resulting inks
were investigated aiming at optimizing the printing process. The shear thinning flow
behavior of the starting suspensions containing 45‒­48 vol% solids and dispersant con-
centrations varying within 0.2‒­0.8 wt% could be well described by the four-­parameter
Cross model. The flow behavior of the suspensions could be correlated with the in-
teraction forces, and the ad-­layer thickness formed around the YSZ particles. Further
adding suitable amounts of a binder and a coagulating agent enabled optimizing the
viscoelastic properties of inks for 3D printing. Good shape retention was observed for
inks with elastic modulus, G′ ≥ 10 MPa. The green scaffolds were dried, sintered at
1350°C, and then used for the assessment of porosity and mechanical properties under
compression tests. The porous structures exhibit average compressive strength (σ) of
~70 MPa. Weibull statistics applied to σ data revealed good reliability of the process,
which can be used to fabricate YSZ scaffolds for orthopedic applications.

KEYWORDS
bone, dispersants, dispersion, processing, robocasting, scaffold

1  |   IN T RO D U C T IO N with limited availability of bone, donor site morbidity, more

A remarkable increase of life expectancy has been witnessed
over the last decades, especially in developed countries,
which brought increasing incidences of bone diseases and
trauma accidents.1–­3 The loss of bone mass due to osteopo-
rosis comes together with an increasing brittleness and the
occurrence of associated breaking events. Aging also brings
increasing incidences of bone tumor resections and of seri-
ous trauma injuries, which also often appear in younger ages
associated with the participation in radical sports, working,
and traffic accidents. These problems demand for suitable
grafting materials and surgical procedures.3–­5 Autografts,
often considered to be the gold standard, are associated
complex surgical procedures, risk of infection, and societal
costs,6–­8 while the allografting option poses potential risks
of disease transmission.6–­9 To address these drawbacks, great
research efforts have been recently devoted towards develop-
ing synthetic bone grafts, which desirably should exhibit a set
of challenging features: mimicking the structural properties
of bones in terms of porosity, interconnectivity, bioactivity,
and mechanical strength.10 The interconnectivity of pores
with appropriate size is essential to allow nutrient/metabolite
transportation and bone tissue ingrowth.11 However, biologi-
cal and mechanical requirements are often conflicting factors
as higher porosity tends to compromise the mechanical stabil-
ity of scaffolds. Accordingly, a proper trade-­off between both

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4368    ©
wileyonlinelibrary.com/journal/jace
2021 The American Ceramic Society J Am Ceram Soc. 2021;104:4368–4380.

GADDAM et al.
criteria must be considered upon designing bone scaffolds.12
Bone grafts based on calcium phosphates13–­15 and bioactive
glasses often satisfy the requirements as bone defect-­filling
materials.16,17 However, the repair of critical-­ size defects
in skeletal parts subjected to load requires stronger ceramic
materials, restricting the range of viable options. The most
common examples include high purity and ultra-­high purity
alumina (e.g., CERALOX),18,19 Zirconia Toughened Alumina
composites (ZTA),20–­22 and Yttria-­stabilized Zirconia (YSZ,
e.g., BIOLOX®delta).15,23
Ceramic scaffolds can be fabricated by several different
methods, such as the polymeric sponge replication method
that provides porous structures mimicking that of trabecu-
lar bones.20,22,24 However, the method and the mechanical
properties of scaffolds derived thereof are difficult to con-
trol. Fortunately, the last decades witnessed a fast transition
trend from analog to digital processes and the emergence
of several additive manufacturing (AM) techniques that
enable overcoming most of the stringent limitations of the
conventional techniques.15,19 Robocasting is a 3D printing
technique that uses a triaxial (XYZ) dispenser to extrude
a viscoelastic paste in a layer-­by-­layer fashion, which has
been used to produce dense and porous structures from sev-
eral materials.12–­14,16,17,20,23 In the case of zirconia,25–­29 the
dispersion of powders and the preparation of printable inks
need further improvements. The relatively low solid load-
ings achieved by Li et al.25 (28  vol%) and by Peng et al.26
(<38 vol%) did not confer satisfactory viscoelastic properties
for printing and would imply extensive and hard to control
shrinkages upon drying and sintering. Liao et al.27 started
from a suspension containing 47  vol% ZrO2, but the max-
imum elastic modulus of the ink (80  kPa) was insufficient
to grant good shape retention to the extruded filaments.
Zirconia suspensions containing 50  vol% solids were re-
ported in other works.28,29 However, the pastes prepared
thereof were used to print bulk ceramic parts in which the
extruded filaments were supported along their entire length,
turning the process less demanding in terms of shape reten-
tion capability. This limitation is even more critical when the
ink undergoes time-­dependent changes in viscoelastic prop-
erties, as expected when starting from a typical traditional
gel casting formulation, also narrowing the useful time win-
dow for printing.29 Multiscaled porous ceramic structures
with interesting strength and stiffness-­to-­density properties
have been fabricated by robocasting from particle-­stabilized
emulsion inks using a 250 μm diameter printing nozzle.30,31
However, the reported elastic moduli (G′ ≤0.1 MPa) are too
small for grating suitable shape retention to filaments ex-
truded through 410  μm diameter. Therefore, this strategy
needs further refinements to overcome its poor ability to
control the viscoelastic properties. These limitations could
be attributed to moderate solid loading (~35 vol%)30 or to a
combination of this factor with an unsuitable selection of the
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   4369
types and amounts of processing additives.31 Using capillary
suspension-­based inks, a somewhat different concept but still
formulated based on two immiscible liquids, Willenbacher
et al.32,33 introduced a processing route for manufacturing
cellular structures with high specific strength. The authors
claim that open porous hierarchical structures spanning over
length scales from 10−3 to 10−7  m can be obtained by this
method. However, the pastes derived thereof share common
features with those prepared from particle-­stabilized emul-
sions: The solid loadings reported are even lower, and the
resulting elastic moduli are too low to enable the filaments
spanning through even short distances and retaining their
shapes. The main challenges in ceramic robocasting have
been recently well summarized by Peng et al.34 explicating
that further studies are required to cover the existing gaps.
Unfortunately, ceramics with multiscaled porous structures,
including significant closed porosity fractions30–­33 that en-
hance the overall porosity volumes, can hardly be thought
as biomedical scaffolds for load bearing applications due to
their insufficient mechanical stability.35,36 This can easily
be deduced from the Rice's formula that exponentially cor-
relates the compressive strength with the porosity volume,
Equation (1):
𝜎 = 𝜎 0 e( − bP) (1)
where σ is the strength at pore volume fraction P, 𝜎 0 is zero-­
porosity strength, and the constant b is related to the pore
characteristics.
This article aims at shedding further light on the correla-
tion between the interaction forces among zirconia particles
and the flow behavior of the suspensions and between the
amounts of processing additives and the viscoelastic prop-
erties of the printing pastes. We also report on the develop-
ment of (a) colloidal inks with high solid volume fractions
(up to 50  vol%) and stiffnesses (elastic moduli ≥10  MPa)
that exhibit good shape retention after extruded into fil-
aments and (b) log pile-­shaped scaffolds with a macropo-
rosity of ~70%, macro pore sizes of ~400 μm, and targeted
minimal microporosity for not impairing their mechanical
performance. Gaining a better understanding of the key fac-
tors for determining the reliability of the fabricating process
and the relevant functional properties of sintered scaffolds:
bone ingrowth ability and mechanical stability for load bear-
ing orthopedic applications.
2  |  EXPERIM ENTAL PROCED U R E
2.1  |  Preparation of zirconia inks
A YSZ (TZ-­ 3YS, TOSOH) powder with a density of
6.05 g cm–­3 and isoelectric point (IEP) in water at pH = 4 and
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4370       GADDAM et al.

a specific surface area of 7 ± 2 m2 g–­1 was used.37 The par-
ticle size (PS) analysis (Coulter LS 230, Fraunhofer optical
model, Amherst) revealed a D50 = 0.43 μm and a distribution
spanning from 0.16 to 3.86 μm.
Different amounts (0.1, 0.2, 0.3, 0.5, 0.8, and 1.0  wt%)
of a relatively short length anionic polyelectrolyte disper-
sant salt derived from ethanolamine and citric acid with an
average molecular mass of 320  g  mol–­1 (Dolapix CE 64,
Zschimmer & Schwarz, Germany) were used to prepare
suspensions with a solid loading of 45  vol% in deionized
water, which were kept rolling overnight on a roller mill. The
suspensions, coded as indicated in Table 1, were tested for
flow properties. The results revealed that 0.3  wt% disper-
sant (S45D0.3) was the most effective. This optimal amount
of dispersant was then chosen to maximize the solid loading,
enabling in achieving suspensions with 48  vol% (S48D0.3)
and 50  vol% (S50D0.3). In the following step of ink prepa-
rations, 2  wt% (relative to the dry mass of the solids) of a
binder/viscosifying agent (hydroxypropyl methylcellulose—­
HPMC) was added in the form of a stock solution contain-
ing 0.436 g ml–­1 to increase the viscosity of the suspension.
The homogenization was performed in a planetary centrif-
ugal mixer (ARE-­250, Thinky Corp.) for a few minutes as
reported elsewhere.14
Finally, different contents (0.00, 0.01, and 0.03 wt% rel-
ative to the dry mass of the solids) of a coagulating agent
(polyethyleneimine-­PEI, ~50  wt% in H2O, Sigma-­Aldrich)
were added to suspensions containing 48  vol% solids and
2 wt% HPMC, followed by homogenization at 1300 rpm for
5 min.19 The aim was to give the inks the viscoelastic prop-
erties needed for printing and confer good shape retention
capability to the extruded filaments. These inks were coded
based on the amounts of solids and processing additives as
indicated in Table 1.
2.2  |  Rheological measurements
The rheological properties of all the suspensions/inks were
assessed using a rheometer (Kinexus Pro+ Rheometer). A
cone-­plate geometry (4°/40 mm) with a gap of 150 μm was
adopted to test the flow behaviors of the starting suspen-
sions. Dynamic mechanical analysis (DMA) on samples
S48D0.3H2P0.00, S48D0.3H2P0.01, and S48D0.3H2P0.03 was per-
formed at frequency of 1 Hz using parallel plates with a gap
of 1 mm to measure the viscoelastic properties of the result-
ant inks.
2.3  |  Three-­dimensional printing scaffolds
by Robocasting
The printed scaffolds consisted of a log pile mesh of rods dis-
pensed in a layer-­by-­layer fashion, using a robotic deposition
device (3-­D Inks). The optimized ink (S48D0.3H2P0.03) was
carefully inserted into a 5-­ml syringe to avoid bubbles for-
mation and then used to produce the scaffolds. The filaments
were extruded through a cylindrical nozzle with an inner di-
ameter of 410 µm (EFD Inc.) at a printing speed of 5 mm s–­1.
The deposition of the rods was made directly into a paraffin oil
bath to avoid nonuniform drying. The process was controlled
by the robotic system according to the CAD model as shown
in Figure 1. Porous cube-­shaped (125 mm3) structures with a
macro pore size of 400 μm were fabricated. The as-­obtained

T A B L E 1   Experimental variables investigated for suspensions and rheological fitting parameters

Suspensions investigated Cross model parameters

Solid
Loading Dolapix HPMC PEI ηo η∞ α tc m R2

Codes (vol%) (wt%) (Pa s) (sm) (s) —­ —­

S45D0.1 45.0 0.1 0.0 0.00 —­ —­ —­ —­ —­ —­
S45D0.2 45.0 0.2 0.0 0.00 372 0.12 1293.37 19019 0.73 1.00
S45D0.3 45.0 0.3 0.0 0.00 182 0.12 108.65 526 0.75 1.00
S45D0.5 45.0 0.5 0.0 0.00 243 0.16 20.00 35 0.84 1.00
S45D0.8 45.0 0.8 0.0 0.00 122 0.28 3.51 4 0.90 1.00
S45D1.0 45.0 1.0 0.0 0.00 —­ —­ —­ —­ —­ —­
S48D0.3 48.0 0.3 0.0 0.00 42215 0.21 28 490 495643 0.78 1.00
S50D0.3 50.0 0.3 0.0 0.00 93816 0.46 27 433 897890 0.75 1.00
S48D0.3H2P0 48.0 0.3 2.0 0.00 4156 0.88 92.90 163 0.89 1.00
S48D0.3H2P1 48.0 0.3 2.0 0.01 —­ —­ —­ —­ —­ —­
S48D0.3H2P3 48.0 0.3 2.0 0.03 —­ —­ —­ —­ —­ —­
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GADDAM et al.   
   4371

F I G U R E 1   CAD model of the scaffold

structure: isometric (left) and lateral (right)
views with the structural parameters of
the mesh [Color figure can be viewed at
wileyonlinelibrary.com]

F I G U R E 2   Flowchart describing the main steps of the scaffold manufacturing process [Color figure can be viewed at wileyonlinelibrary.com]

scaffolds were removed from the oil and dried at room tem-
perature and then submitted to a heating rate of 1°C min–­1 up
to 600°C, with soaking time of 1 h to remove the organic ad-
ditives. After that, the scaffolds were sintered at 1350°C for
1 h using a heating rate of 5°C min–­1 and then cooled down to
room temperature.
Figure 2 presents a schematic of the entire experimental
procedure, showing the step-­by-­step methodology used in
the preparation of the scaffolds starting from the YSZ pow-
der and processing additives to develop the printing inks,
Robocasting to sintering of the scaffolds.
2.4  |  Physical characterization
of the scaffolds
2.4.1  |  Porosity, mechanical properties, and
Weibull statistics
The apparent density of each scaffold was calculated
from its weight (after oven drying at 110°C and cool-
ing to room temperature in an exicator) and its appar-
ent volume measured by the Archimedes principle. Each
weighted sample was put in one of sequentially numbered
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4372       GADDAM et al.

flasks containing water. The flasks were put in an ultra-
sonic bath for a few minutes to facilitate the removal of
any air bubbles residing inside the porous structures and
kept there for at least 2  h before measuring the weight
of the displaced fluid upon moving each sample to the
Archimedes balance apparatus. The weight of each wet
sample was measured after removing the excess water
from the external surface and from the internal pores
with an absorbent paper, complemented by a quick blow
of compressed air. The microporosity ( p) was calculated
according to Equation (2),
𝜌s
p=1−
𝜌th
Here, 𝜌th is the theoretical density of zirconia (6.05 g cm–­3)
and 𝜌s is the density measured by Archimedes principle. The
macroporosity (MP) of the scaffolds was determined accord-
ing to Equation (3):
𝜋d 2 shear rate (𝛾̇ )) of the 45 vol.% suspensions (S45D0.1–­S45D1.0)
MP ≈ 1 −
4hs
The parameters s, h, and d are defined in Figure 1. The
total porosity of the scaffolds sintered at 1350°C was taken
as the sum of ( p + MP).
The compressive strength values (σ) of sintered scaf-
folds were determined using a universal testing machine
(Shimadzu Autograph AG 25 TA) with a maximum load
capacity of 10  kN at room temperature (RT). The load
was applied perpendicular to the printing plane at con-
stant speed of 0.5 mm min–­1, and the maximum measured
value for each sample was divided by its area to obtain σi.
The Weibull statistical analysis was performed using the σi
data of 25 samples. The Weibull reliability (R(σ)), hazard
functions (h(σ)), and mode (σm) are given by the following
equations38:
[ ( )m ]
𝜎
R (𝜎) = exp −
𝜎0
2.4.2  |  Sintered microstructure and
morphological analysis
The microstructural and morphological features of the sin-
tered pellets and scaffolds were accessed by SEM analysis
(Hitachi SU-­70, Hitachi High-­Technologies Europe, GmbH).
Before observation, the samples were placed on metallic sup-
ports and sputter coated with carbon under an acceleration
voltage of 15 kV and a beam current of 10 µA. The scaffolds
were also examined on a stereo microscopy (SM, Stereo
Microscope with LED and HD Camera LEICA EZ4HD,
Germany).
(2)
3  |  RESULTS
3.1  |  Rheological behavior of the starting
suspensions
Figure 3A displays the flow curves (viscosity (𝜂) versus
(3)
with different added amounts of dispersant (Table 1). The
suspension with the lowest added amount of dispersant,
S45D0.1, exhibits a shear thinning behavior up to a shear rate
of ~30  s–­1, followed by shear-­induced flocculation up to a
maximum viscosity of ~35 Pa.s and a subsequent slippage.
All the other flow curves are shear thinning, an essential fea-
ture for extrusion-­based 3D printing. A gradual upshift of the
flow curves with increasing amounts of dispersant is clearly
observed up to S45D0.8−S45D1.0, which are almost coinci-
dent, except for shear rates ≤1 s–­1 where S45D1.0 exhibits a
near-­zero shear viscosity plateau. As stated in Section 2.1,
0.3 wt% dispersant was selected for the preparation of inks.
To quantitatively understand the rheological behavior, the
viscosity curves were tentatively fitted with different existing
models. Among them, the three-­parameter Sisko39 model and
a four-­parameter Cross40 model, respectively, described by
Equations (7) and (8) revealed good fitting capabilities, the
best fitting being observed with Cross model.
(4)
̇ = 𝜂 ∞ + k𝛾̇ n − 1
𝜂 (𝛾) (7)

( )( )m − 1
m 𝜎 𝜂o − 𝜂∞
h (𝜎) = (5) ̇ = 𝜂∞ +
𝜂 (𝛾) (8)
𝜎0 𝜎0 1 + 𝛼 𝛾̇ m

Here, ηo is the viscosity at zero shear rate, η∞ is the vis-

) m1
1 (6) cosity at infinite shear rate, k is a constant, α is a structural
(
𝜎m = 𝜎0 1−
m parameter related to the shear rate dependent breakdown of
the structure, and n and m are dimensionless exponent param-
Here, m is the shape parameter, also called Weibull modu- eters related to the degree of shear thinning. Moreover, the
lus, and σ0 is the scale parameter that is related to the average time constants for Cross (tc) and Sisko (ts) models could be
value of the distribution. written as follows:

GADDAM et al.
F I G U R E 3   (A) Effects of different amounts of dispersant on the
flow behavior of zirconia suspensions containing 45 vol% solids. (B)
Fitting of the rheological data in (A) with Cross model [Color figure
can be viewed at wileyonlinelibrary.com]
tc = 𝛼 m
1
(9)
1
ts = k n − 1 (10)
Since the Sisko and Cross models cannot capture the
anomalies observed for S45D0.1 and S45D1.0 suspensions,
particularly the dilatant behavior of S45D0.1, only the flow
data of S45D0.2, S45D0.3, S45D0.5, and S45D0.8 suspensions
were fitted with these models. Although the Sisko model
could reasonably describe experimental data (Figure S3 in
the supporting information), an excellent fitting was ob-
tained with the Cross model, as disclosed in Figure 3B.
The rheological behaviors of suspensions with solid load-
ings up to 50  vol% (Table 1) are displayed in Figure 4A.
Incrementing the solid contents and adding binder caused
clear upshifts of the flow curves. The suspension S50D0.3
exhibited a strong shear induced flocculation for shear rates
>100  s–­1, which noticeably slows down the rotating cone
(Figure 4A). Accordingly, only the suspensions containing
solid loadings up to 48  vol% could very well fit the Cross
model, as shown in Figure 4B and Table 1.
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   4373
F I G U R E 4   (A) Influence of solid loading on the flow behavior
of zirconia suspensions containing fixed amounts of dispersant and
binder. (B) Fitting of the rheological data in (A) with Cross model
[Color figure can be viewed at wileyonlinelibrary.com]
3.2  |  Viscoelastic properties of the
printing inks
The curves of storage moduli of the samples S48D0.3H2P0.00,
S48D0.3H2P0.01, and S48D0.3H2P0.03 versus complex shear
stress measured at frequency of 1  Hz are displayed in
Figure 5. The samples contain fixed amounts of solids,
dispersant, and binder, without/with increasing addi-
tions of the coagulating agent (Table 1). Figure 5 shows
a dramatic dependence of the elastic modulus (G′) with
increasing additions of PEI, being very sensitive even to
small increments, demonstrating its effective coagulating
effect with cationic species bridging the anionic dispersant
groups adsorbed at the surface of the particles. In the ab-
sence of PEI, G′ shows a slightly descending ramp from
~3.5−3.0 kPa when the complex shear stress changes from
~10−70  Pa, followed by an accentuated disruption of the
internal structure upon further increasing the shear stress.
The stiffness of the inks increased for more than 1.5 and 3.5
orders of magnitude upon adding just 0.01 and 0.03  wt%
of PEI, which also prolonged the linear viscoelastic region
up to ~80 and >100 Pa, respectively. The highest stiffness
of the S48D0.3H2P0.03 ink confers enhanced shape retention
 |
4374       GADDAM et al.
capability to the extruded filaments, justifying its selection
for the scaffold's fabrication.
3.3  |  Scaffolds’ characterization
Scaffolds with a macro pore size of 400 μm were fabricated
from the optimized ink. The scaffolds underwent a shrinkage
of 14.570 ± 0.002% upon sintering. The optical microscopy
image of the sintered scaffolds shown in Figure 6A reveals a
good shape regularity and straight geometry of the rods. The
surface microstructure of the sintered scaffolds presented in
Figure 6B reveals that a good degree of densification was
achieved.
The bulk density of the sintered filaments mea-
sured by Archimedes method gave an average value of
6.000  ±  0.034  g  cm−3, which is very close to the theoreti-
cal density of zirconia (ρ  =  6.05  g  cm−3). This means that
the microporosity resulting from the burning of organics and
incomplete sintering can be neglected. The measured macro-
porosity, 69.820 ± 0.008%, is in good agreement with the val-
ued of 70% intended for the scaffold model shown in Figure
1. The relatively high degree of densification of the zirconia
F I G U R E 5   Dynamic mechanical analysis for systems containing
fixed amounts of solids, dispersant, and binder, without and with
increasing additions of the coagulating agent [Color figure can be
viewed at wileyonlinelibrary.com]
(A) (B)
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scaffolds and their morphological features are promising for
applications in bone tissue engineering. This is confirmed by
the Weibull analysis of the Σ data presented in Figure 7. The
modal value of σm is 70.71 MPa, and the parameters m and
σ0 were calculated to be 6.05 and 72.85 MPa, respectively.
4  |  DISCUSSION
4.1  |  Preparation and rheological
characterization of the starting suspensions
An accurate control of rheological properties is key to the
preparation of inks for AM. The structure of a suspension at
the lowest scale (a scale that is reverent for studying the flow
behavior) consists of individual particles (IPs). At a slightly
higher scale, the IPs cluster/agglomerate and create larger
structures called flocs. At a given shear rate, there will be a
steady-­state size distribution of the flocs. This steady state is
established when the rate of IPs added to the cluster is equal
to the rate of IPs removed from the cluster for a given shear-
ing conditions. An increasing shear rate induces increasing
hydrodynamic stresses on the flocs, which in turn result in
a smaller equilibrium size distribution. Consequently, such a
suspension will exhibit a shear thinning behavior. This ex-
plains why the suspensions with different amounts of disper-
sant (Figure 3) all showed shear thinning behaviors.
Anionic polyelectrolytes are often used as dispersants to
stabilize colloidal suspensions, creating electrosteric repul-
sions between the IPs, as schematized in (Figure 8A). The
specific interactions between the particles’ surface and the
polyelectrolyte ions depend on a number of factors.41 The
pH of the dispersing medium determines the dissociation ex-
tent of the functional polyelectrolyte groups and the stretch-
ing of adsorbed chains towards the solution, as sketched
in Figure 8B. The particles’ surface chemistry (IEP) de-
termines the affinity of polyelectrolyte chains towards ad-
sorption, their adsorption density, and the flow properties
of the suspensions. For example, aqueous suspensions con-
taining 45 vol% alumina (IEP = 9, D50 = 0.57 μm), or YSZ
(IEP = 4, D50 = 0.48 μm), or silica (IEP = 2, D50 = 0.60 μm)
F I G U R E 6   (A) Optical microscope
image of a sintered scaffold fabricated by
robocasting. (B) SEM image showing its
surface microstructure [Color figure can be
viewed at wileyonlinelibrary.com]

GADDAM et al.
that were dispersed with 1 wt% of the same dispersant used
in this work, all exhibited shear thinning.37 However, they
strongly differed concerning the shear rate dependence of
shear stress and viscosity, which decreases in the order: sil-
ica >YSZ>alumina. Under low shear rates (𝛾̇ ~1  s–­1), the
viscosities of YSZ and silica suspensions were, respectively,
about 1 and 2 orders of magnitude higher in comparison
to that of alumina. Moreover, the percentages of theoretical
density (%TD) of green bodies consolidated by epoxy gel
casting from suspensions containing 10  wt% epoxy resin
decreased from 62.6 ± 0.2 (alumina) to 57.0 ± 0.2 (YSZ)
and 52.2 ± 2.7 (silica). Therefore, the added amount of dis-
persant, its adsorption density, and the partition between
adsorbed and nonadsorbed (or in excess in the solution)
play important and complex roles on colloidal processing.
The same applies to the physical features, including average
PS, particle size distribution (PSD), which determine the
surface area available for adsorption. As a matter of fact,
the effectiveness of dispersants scales with the surface area
of the particles in suspension.28,42–­45 Even though, in most
of the works published, the dispersant amounts are usually
F I G U R E 7   Weibull plots (Weibull analysis of the compressive
strength of the zirconia scaffolds). The dots represent 25 experimental
compressive strength values [Color figure can be viewed at
wileyonlinelibrary.com]
F I G U R E 8   Schematic illustrations of (A) electro steric stabilization mechanism. (B) influence of pH on the configuration of adsorbed anionic
polyelectrolyte species on an ideal ceramic surface and on the resulting ad-­layer thickness (δ) (adapted from previous study34). At low pH, the
polyelectrolyte chains are nondissociated, do not repel each other, and δ is small; while at high pH, they are fully dissociated, repel each other, and
stretch towards the solution forming and δ increases [Color figure can be viewed at wileyonlinelibrary.com]
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   4375
referred to in wt.% relative to the dry mass of solids. This is
acceptable especially for monodispersed powders or pow-
ders exhibiting relatively narrow PSD. For example, assum-
ing spherical particles of uniform size, the specific surface
area (SSA) is given by Equation (11):
6
SSA = (11)
𝜌d
with ρ = density (Mg⋅m−3) and d = particle diameter (m).
All these physical features altogether determine the average
interparticle separation distances at which they may begin
to “feel” each other's presence.
The range of surface forces depends on the stabilization
mechanism. Electrostatic forces are known to extend their
action up to longer distances in comparison to the shorter
range steric ones, restricting the maximum achievable sol-
ids volume fraction.46 Therefore, a polyelectrolyte dispersant
with attenuated electrostatic component combined with ste-
ric repulsion forces is expected to promote a better-­balanced
electrosteric stabilization of IPs. In any case, the thickness (δ)
of the ad-­layer (adsorbed/hydrated layer) formed around the
IPs, increases their apparent size, as shown in (Figure 9A).
As a consequence, the actual solids’ volume fraction (φ) in-
creases to an effective volume fraction (φeff), as given by the
following equation (assuming the particles are spherical with
radius r),41
𝛿 3 (12)
( )
𝜑eff = 𝜑 1 +
r
For a given oxide surface and fixed pH of dispersion me-
dium, the incremental size depends on dispersant's concen-
tration, as schematically illustrated in (Figure 9B–­D). This
explains the lower viscosity values measured for suspensions
with moderate solid loading and with the smaller added
amounts of dispersant (S45D0.1−S45D0.2), as observed in
Figure 3. The flocculation observed for the S45D0.1 system for
𝛾̇  ≥ 30 s–­1 cannot be attributed to “bridging flocculation”,41
 |

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4376       GADDAM et al.

F I G U R E 9   Schematic illustrations about the influence of the added amount of dispersant on adsorption density, configuration of adsorbed
anionic polyelectrolyte chains and the resulting ad-­layer thickness (δ): (A) insufficient surface coverage; (B) optimal added amount of dispersant;
(C) excessive amount of dispersant; (D) the ad-­layer thickness increases the apparent size (r + δ) of dispersed particles and influences the flow
behaviors of the suspensions [Color figure can be viewed at wileyonlinelibrary.com]

a phenomenon that happens when the particles’ surface is
only partial covered with long polymer/polyelectrolyte spe-
cies. Under these circumstances, the long chains can adsorb
onto the surfaces of different IP establishing bridges that
borrow the name to this flocculation mechanism.41 Bridging
flocculation was successfully explored for the first time
in the preparation of 3D printing inks of 45S5 bioglass by
Robocasting using high molecular weight (250 000 g mol–­1)
sodium carboxymethyl cellulose (CMC) as single processing
additive.47,48 In the present case, the chain length of Dolapix
(320  g  mol–­1) is too short to allow the formation of free
segments (loops and tails) capable of bridging different IP.
Instead, it adopts an airy-­like configuration extending to short
distances at which steric interactions prevail to enable high
solids loading to be achieved, as demonstrated elsewhere.46
The flocculation observed for the S45D0.1 system for
𝛾̇  ≥ 30 s–­1 can be attributed to an insufficient particles’ surface
coverage by the dispersant species. Under shear, the uncovered
surface patches are forced to collide with each other and are
likely to stick and coagulate under the shear induced IP col-
lisions. As soon as this coagulation phenomenon is triggered,
increasing shear stresses are necessary to continue deforming
the system, inducing a dramatic increase in the number of col-
lisions among IP. This translates in an abrupt augmentation of
the resistance to flow and is known as shear-­induced floccula-
tion. This phenomenon can be prevented when the surface cov-
erage by the dispersant is enough to keep the IP apart by the
repulsive forces, making the system to behave shear thinning.
Among the smooth shear thinning flow curves, the one
corresponding to S45D0.2 exhibits the lowest viscosity, mean-
ing that 0.2 wt% would be the most effective one for this sol-
id's concentration. This result contrasts with the observations
reported by Liu et al.49 that adding increasing amounts of
Dolapix CE 64 enhances the stability of the suspensions when
the solid loading was kept constant. However, with increas-
ing solids loading, the IPs are forced to approach each other,
and higher amounts of dispersant (≥0.3 wt%) were required
to prevent flocculation under shear. Therefore, 0.3 wt% was
the most effective dispersant concentration for φ > 45 vol%
(Figure 8C).
According to Krieger,50 the relationship between the rel-
ative viscosity (ηr) of the suspension and the volume fraction
of the solids is given as follows:
𝜑eff − [𝜂]𝜑m
( )
(13)
𝜂r = 1 −
𝜑m
Here, φm is the maximum volume fraction of solids and
[η] is the intrinsic viscosity which is Einstein's limit of vis-
cosity in a very dilute suspension which typically takes the
values 2.5–­3.0. Equation (13) is a monotonically increasing
function. From Equations (12) and (13), one can easily infer
how the ad-­layer thickness influences the suspension viscos-
ity, as schematized in Figure 9B–­D. Therefore, it is important
to understand how the added amount of dispersant influences
the ad-­layer thickness and the rheological properties in order
to tune the quality of colloidal processing.
The dispersant used in the current study promotes both elec-
trostatic and steric effects as shown schematically in Figures 8
and 9. First, let us consider only the electrostatic interactions.
The ad-­layer around an IP created by electrostatic interactions is
called electrical double layer (EDL). The effect of an electrolyte
concentration on the EDL thickness (also called Debye length)
is described by Debye–­Hückel theory. The Debye length is
generally represented by the symbol κ–­1 in the literature and is
inversely proportional to the square root of the ionic strength.
For a given (poly)electrolyte, κ–­1 is inversely √proportional to
the concentration (c) of the solution (𝜅 − 1 ∝ 1∕ c). Therefore,
adding dispersant to the suspension tends to reduce the EDL
thickness as schematized in Figure 10A. The more extended
EDL thickness in the case of the S45D0.1 suspension explains
its higher stability and slightly lower measured viscosity values

GADDAM et al.
for shear rates ≤40 s–­1 (Figure 2). However, under higher defor-
mation rates, IPs with larger apparent sizes collide more often
with each other instead of smoothly sliding, therefore offering
an increasing resistance to flow. This explains the subsequent
shear-­induced flocculation and irregular flow curve observed
for shear rates ≥30 s–­1 (Figure 3). Now if we consider just the
steric interactions, the ad-­layer thickness depends on the num-
ber density of the chains adsorbed at the surface of the IP. When
the concentration of the chains present in the solution is low, the
number density at the surface is also low (Figure 9). However,
as the concentration of the chains increases, the number den-
sity gradually increases until the surface becomes saturated.
Therefore, adding a purely polymeric dispersant increases the
thickness of the ad-­layer up to a certain threshold limit (Figure
10A). In the case of a polyelectrolyte dispersant, both the
above-­mentioned phenomena would be simultaneously at play.
Therefore, if the steric effect is dominant, one would expect an
increase in the ad-­layer thickness. Conversely, if the electrostatic
effect is dominant, the ad-­layer thickness should decrease. In
the current study, suspensions with increasing amounts of dis-
persant showed an overall increasing trend of viscosity (Figure
3) suggesting a dominant steric effect for the systems S45D0.2−
S45D1.0. Moreover, the threshold saturation limit for adsorption
onto the surface of IPs seems to have been achieved at 0.8 wt.%
dispersant, explaining why no further increments in viscosity
were registered upon increasing the dispersant concentration to
1 wt%. This can be understood considering that Dolapix CE 64
is an ethanolamine salt of citric acid with an average molecular
weight of 320 g mol–­1,51 therefore, prone to assume an airy-­like
configuration when adsorbed, due to the mutual electrostatic
repulsive interactions among the dissociated anionic groups.
Neighboring IP with such airy-­like configuration will undergo
some interpenetration of the adsorbed layers as reported else-
where.47 This will lead to some internal structuration under
near-­rest conditions, explaining the near-­zero shear viscosity
plateau of S45D1.0 for shear rates ≤1 s–­1.
Besides, the parameter tc (Equation (9)) is a measure of the
size of IP clusters at the initial plateau region before the onset
of the shear thinning behavior.40 Larger values of tc means that
shear thinning occurs at lower shear rates and vice versa for
F I G U R E 1 0   Schematics of (A) the
polyelectrolyte concentration dependent
contributions of Steric and electrical double
layer (EDL) forces to the ad-­layer thickness.
(B) Interparticle potentials with a fixed
polyelectrolyte concentration [Color figure
can be viewed at wileyonlinelibrary.com]
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   4377
smaller values of tc. Increasing amounts of dispersant lead to
decreasing values of tc (Table 1). This suggests that the addi-
tion of dispersant increases the stability and leads to the forma-
tion of smaller flocs. Therefore, these flocs only break apart at
a higher shear rate. The interaction energy between the IPs to
form flocs primarily has three contributions: (1) EDL, (2) Van
der Waals’, and (2) steric interactions (Figure 10B). The com-
bination of the first two interactions is described by DLVO
theory (VDLVO). The addition of the dispersant increases the
depth of the secondary minimum of the VDLVO. When the sta-
ble suspension is at rest or under low shear rates, IPs exist in
this secondary minimum, resulting in weak flocculation.
Increasing the solids loading while keeping the amount of
dispersant constant induced increments in suspension's vis-
cosity (Figure 4). This is an expected result, as predicted by
Equation (13). The values of tc also increase with incremental
amounts of solids. This can be attributed to the shorter aver-
age distances among IPs and the higher frequency of their
mutual collisions under shear.
4.2  |  Preparation and rheological
characterization of printable inks
The addition of HPMC increases the intrinsic viscosity of the
dispersion liquid and prevents segregation of particles, thus
preserving the structure of the suspension for longer periods
due to the intertwining long-­chain molecules. This effect can
be seen in the lowering of the tc value from ~5  ×  105  s in
S48D0.3 to 163 s in S48D0.3H2P0.00 (Table 1). The addition of
PEI significantly enhances the elastic properties of the inks,
making them suitable for printing (Figure 5). Elastic moduli
of the printing inks within the range of 1–­10  MPa are usu-
ally required for good shape retention of the extruded fila-
ments.40 Since the sample S48D0.3H2P0.03 exhibits a constant
elastic modulus of ~11 MPa over a long range of shear stress,
this sample was chosen for direct ink writing. The ability of
the ink to recover its internal structure is another important
after-­printing criterium for shape retention capability of the
printed parts, as recently demonstrated by the authors upon
 |
4378       GADDAM et al.
3D printing free-­standing pillar arrays vertically.52 Other au-
thors struggled to find suitable printability predictors. The
one proposed by Smay et al.53 is expressed as follows:
G′ ≥ 1.4𝛾s4 D (13)
where γ is the specific weight of the ink 𝛾 = 0.25 𝜌ink − 𝜌oil g,
[ ]
with 𝜌ink and 𝜌oil being the density values of the ink and oil,
respectively; s is the reduced span distance (L/D), with L
being the distance between the centers of two adjacent fila-
ments, and D the filament diameter.
When applied to our ink S48D0.3H2P0.03 [𝜌ink = 3442 kg m−3;
𝜌oil = 762 kg m−3; s = (810/410); D = 410 μm; g = 9.81 m s−2],
the above equation gives G′  ≥  78  Pa. This value is at least
6 orders of magnitude lower than the elastic modulus of the
inks used for printing. Acknowledging the inability of the
Smay et al.53 criterium for predicting the printability of high-­
density pastes, Franks et al.30 proposed alternative relations
based on plots of storage modulus against yield stress, includ-
ing empirical (not dimensionless) constants, C1 [Pa]2, and C2
[Pa]3. The latter one considers the recovery of Gʹ as a function
of time after cessation of shear. According to these authors,
pastes that do not recover to at least about 10 kPa, within the
first 15  s after deposition will slump. However, empirical
relations supported by experimental observation in a given
system might be applied with caution to other systems, as em-
pirical relations are not necessarily supported by theory. But
the ability of the ink to recover the internal structure as a func-
tion of time after cessation of shear is a very important after-­
printing criterium recently demonstrated by Ferreira et al.52
Other articles dealing with DIW34 just mentioned the print-
ability criteria proposed by Smay et al.,53 or did not consider
any printing criterium.31 However, the elastic moduli of their
inks in the absence of propionic acid were ~0.01 MPa (three
orders of magnitude smaller than that of our S48D0.3H2P0.03
ink). Upon adding 0.08 mmol of propionic acid, G′ increased
to ~0.1 MPa, still much below the desired range of 1–­10 MPa.
4.3  |  Characterization of the
sintered scaffolds
The Weibull statistical analysis of the compressive data of the
sintered scaffolds (Figure 7) shows a high Weibull modulus
of ~6 suggesting a good reliability of the printing process and
of the experimental parameters employed. Moreover, it shows
Weibull strength of ~70 MPa, which is high enough for the bio-
medical applications that require some load bearing capability.
According to finite element analysis, the maximum loads expe-
rienced by the human femur bone in standing posture would be
less than 40 MPa even for obese people.54 And for an average
human, the maximum loads experienced during activities such
as standing, walking, jumping, and running are 29, 35, 39, and
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62 MPa, respectively.55 The hazard function (Figure 7) shows
that for loads less than 40  MPa, the probability of failure is
almost zero and for loads between 40 and 60  MPa it is less
than 10%. These results show that the printed materials would
perform exceptionally well in human physiological load bear-
ing functions. The optimized processing conditions enabled
obtaining zirconia scaffolds with good sintering ability, high
shape regularity, and surface smoothness as shown in the im-
ages of Figure 6A. The measured bulk density (6.000 ± 0.034)
is not far from the theoretical density of zirconia, indicating a
microporosity of about 0.82 ± 0.01%, which is confirmed by
the SEM observation of the sample (Figure 6B).
The main shortcomings of the previous works dealing DIW
of zirconia25–­29 were well pointed out in the Introduction part
that deals with relative solid volume fractions of 28  vol%25
and <38 vol%.26 Such low solid loadings did not confer sat-
isfactory viscoelastic properties for printing, implying exten-
sive and hard to control shrinkages upon drying and sintering,
which commonly induces crack formation. This helps ex-
plaining the reduced values of σ of 8 and 10 MPa measured
by Li et al.25 for structures with 63% and 50% porosity, re-
spectively. Peng et al.26 printed dense ceramics and porous
zirconia structures with 45% porosity with flexural strengths
(FSs) of 242.8 ± 11.4 MPa and 57.3 ± 5.2 MPa, respectively.
Our scaffolds with a higher porosity (~69%) exhibit superior
mechanical performance (σ ~70  MPa). Liao et al.27 used a
suspension with 47 vol% ZrO2, but the G′ value (80 kPa) re-
ported for the ink was insufficient to grant good shape re-
tention to the extruded filaments, as well evidenced in their
Figure 4. Such porous structures were not proper for mechan-
ical characterization, and this might be the probable reason
why the authors did not report any mechanical performance
data for the sintered scaffolds. In the works,28,29 bulk ceramic
parts were printed from zirconia inks containing 50 vol% sol-
ids. Only FS data were reported for two groups of samples:
232.8 ± 55 MPa (group 1) and 278 ± 59 MPa (group 2). 28
While in the other work,29 the authors only mention the aver-
age transverse rupture strength value 450 MPa for the sintered
parts. Therefore, a straightforward comparison between the σ
measured for our scaffolds and mechanical performance data
reported in these last works28,29 cannot be made. The compar-
ison of our σ values is impossible in the case of Liao et al.,27
who did not provide any mechanical performance data.
There is still no consensus about the influence of mi-
croporosity on the osteogenesis of scaffolds for bone tissue
engineering.56 On the other hand, eliminating the micropo-
rosity through processing and sintering offers margin to fur-
ther enhance the mechanical properties of the YSZ scaffolds.
This approach is being explored in the frame of a “brother
work” aiming at reducing the critical flaw sizes and compen-
sating for the relatively high macro porosity fraction (~69%)
and macro pore sizes of ~400 μm that are suitable for bone
ingrowth.57,58

GADDAM et al.
5  |   CO NC LUS ION S
Porous YSZ scaffolds with macro porosity features and
mechanical properties suitable for bone tissue engineering
applications were successfully and reliably produced by
Robocasting. A shear thinning behavior of the starting sus-
pensions is an essential requirement to prevent the clogging
of the fine extrusion nozzles during printing. Increasing the
surface coverage of the particles by the short polyelectro-
lyte chains induced an initial fluidization trend up to a mini-
mum according to the viscosity versus shear rate curves due
to a continuous increase of repulsive forces. Adding further
amounts of dispersant beyond this point leads to an increase
of the ad-­layer thickness and concomitant increases in ap-
parent size of IPs. These small-­scale changes translate into
enhanced macro-­resistances of the resulting suspensions to
flow under deformation. Therefore, understanding the spe-
cific roles of the most relevant experimental variables is
key to optimize the fabrication process. The elastic modu-
lus (G′ ~11 MPa) of the optimized ink (S48D0.3H2P0.03) is
high enough to confer shape retention capability, enabling
fabrication of defect-­free scaffolds with good sintering abil-
ity and suitable macroporosity features for bone ingrowth.
Weibull analysis revealed a modal σ of ~70 MPa and a reli-
ability modulus of 6. The produced scaffolds are promising
for orthopedic and bone tissue engineering applications.
ACKNOWLEDGMENTS
This work was developed within the scope of the project CICECO-­
Aveiro Institute of Materials, FCT Ref. UID/CTM/50011/2019,
financed by national funds through the FCT/MCTES.
ORCID
Anuraag Gaddam  https://orcid.org/0000-0002-4266-6092
Daniela S. Brazete  https://orcid.org/0000-0002-5024-3321
Ana S. Neto  https://orcid.org/0000-0002-8083-5758
Bo Nan  https://orcid.org/0000-0002-6580-7273
José M. F. Ferreira  https://orcid.org/0000-0002-7520-2809
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SUPPORTING INFORMATION
Additional supporting information may be found online in
the Supporting Information section.
How to cite this article: Gaddam A, Brazete DS, Neto
AS, Nan B, Ferreira JM. Three-­dimensional printing of
zirconia scaffolds for load bearing applications: Study
of the optimal fabrication conditions. J Am Ceram Soc.
2021;104:4368–4380. https://doi.org/10.1111/
jace.17874