Ceramics International xxx (xxxx) xxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Controlling properties of ceramic formulations for porcelain robocasting

L.S.O. Pires a, b, c, *, J. Luís a, b, M.H.V. Fernandes b, c, M. Oliveira a, b
a
EMaRT Group - Emerging: Materials, Research Technology, School of Design, Management and Production Technologies Northern Aveiro, University of Aveiro, Estrada
do Cercal, 449, Santiago de Riba-Ul, 3720-509, Oliveira de Azeméis, Portugal
b
CICECO, Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193, Aveiro, Portugal
c
Department of Materials & Ceramic Engineering, University of Aveiro, Campus Universitário de Santiago, 3810-193, Aveiro, Portugal

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

Keywords: Porcelain pastes (PlotPastes) were formulated to be used on an additive manufacturing (AM) process (material
Porcelain extrusion) process, primarily robocasting (R3D) technique. The material morphological and thermal character­
Robocasting (R3D) istics were evaluated by scanning electron microscopy (SEM), differential thermal analysis (DTA) and ther­
Additive manufacturing (AM)
mogravimetric analysis (TGA). The rheology and the electrical potential of the ceramic particles were also
Rheology
studied to select and adequate the porcelain paste properties to the R3D AM technique. It was found that shifting
the pH values to acidic, the surface charge of the particles changes and increases the pastes viscosity due to
agglomeration effects. This behaviour was exploited to optimize the paste rheological behaviour which resulted
in the optimum pH at 1.94 (PlotPaste 5). This paste was used in the study of R3D operating parameters. It was
found that small variations in pressure and speed affects the dimensional accuracy of the printed models. The
results showed the disruptive potential of porcelain R3D in the production of customized ceramic products.

1. Introduction necessary to apply heat treatments to obtain useable solid parts.

Recent changes in the industrial paradigm helped spread additive
manufacturing (AM) technologies at industrial level, which makes them
easily found in many diverse fields, that range from engineering, med­
ical, education, decoration or even toys. AM is then a set of processes
that rely on state-of-the-art technologies to produce, layer-by-layer,
physical products from digital virtual models [1].
According to technological characteristics and material process
ability, AM [2] is classified into seven major processes: i) binder jetting;
ii) direct energy deposition; iii) material extrusion, material jetting; iv)
powder bed fusion; v) sheet lamination and vi) vat photopolimerization
[3–6]. The uniqueness of AM technologies stems from the advantage
that can be taken from the specific properties of the material and its
particular processing characteristics.
There are several extrusion-based AM technologies that can deliver a
real physical model by extruding a filament from a solution, a gel or
paste, such as Direct Ink Writing (DIW) and Robocasting (R3D). The
presence of a bonding liquid material allows a better linkage between
layers, resulting in printed parts of higher density. However, the typical
mechanical anisotropy of materials obtained by extrusion technique is
not solved for ceramic materials. After the parts production, it is
Therefore, it is necessary and highly advised the development of raw
formulations with high solids content [7–11].
The awareness in ceramic industry for AM technologies is growing
due to several factors like software advancements, new dedicated
ceramic equipment with faster production cycles, process control and
improved free form design.
Traditional ceramic industry has potential for implement and
spreading AM technologies. AM potential and characteristics align
extremely well with the ceramic materials process. The experience of
ceramic tableware industry in the application of slurries, pastes and
powders in traditional techniques (e.g. hand craft modelling, pressing
modelling, slip casting, extrusion moulding, jiggering and jollying
moulding methods, isostatic pressing) can bring advantage in the use of
advanced technologies, like AM.
There are some manual processes such as handicraft that allow the
manufacture of custom pieces. This process allows the production of
single or small-scale parts and does not require the manufacture of
specific tools, but presents formal limitations, rigor and reproducibility.
The slip casting process is suitable for manufacturing small units (up to
100 units per mould) but requires the use of moulds and involves the
production of large quantities for mass customization. In this context,

* Corresponding author. Estrada do Cercal, 449, Santiago de Riba-Ul, 3720-509, Oliveira de Azeméis, Portugal.
E-mail address: liliana.pires@ua.pt (L.S.O. Pires).

https://doi.org/10.1016/j.ceramint.2022.09.366
Received 27 June 2022; Received in revised form 23 September 2022; Accepted 29 September 2022
Available online 5 October 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: L.S.O. Pires, Ceramics International, https://doi.org/10.1016/j.ceramint.2022.09.366
L.S.O. Pires et al. Ceramics International xxx (xxxx) xxx

application of AM technologies is justified and can bring value at in­ Table 1

dustrial level [12]. PlotPastes composition and respective pH.
Although the R3D study and application records date back to 1997, PlotPastes Solids H2O Dolapix H₂SO₄ pH
major technological developments have been only occurring in recent
(wt.%) (wt.%) (wt.%) (wt.%)
years [13]. This technology began to be explored intensively in bio­
ceramic materials for tissue engineering and in non-technical ceramic 1 67.74 31.90 0.36 0.00 7.04
2 67.45 32.02 0.36 0.02 5.28
materials for the construction industry [14–20]. Beyond scientific 3 67.31 32.05 0.36 0.07 3.66
dedicated studies, some experiments of designers have also used R3D to 4 67.02 32.09 0.36 0.11 3.40
manufacture creative clay products [12,21–24]. 5 66.31 32.10 0.36 0.18 1.94
R3D uses pastes or suspensions/slurries with high solids content 6 65.34 33.50 0.35 0.35 1.39
7 64.93 34.17 0.35 0.51 1.12
(volume % solids higher than 45), with a pseudoplastic rheological
behaviour for short consolidation time during the construction process.
If the solids content is near 63%, the mobility of the particles is reduced compounds.
inducing an increase in viscosity - dilatant rheological behaviour [9–11,
25]. To prepare the formulations for R3D, it is necessary to take into
2.2. Characterization of formulations
account some required specifications [13,25–31]: i) a pseudoplastic
behaviour to allow the flow through a small hole (nozzle) and at mod­
The morphological characteristics of spray dried powders were
erate shear rates; ii) rheological characteristics that permit the forma­
observed by scanning electron microscopy (SEM) in a Hitachi, Model
tion of a stable deposition, with retention capacity form (without
S4100 equipment. From the SEM images, the particle mean size was
dispersion) after deposition; iii) ability to support multiple overlapping
determined by averaging the diagonals of 600 random particles.
layers, without defects, to form a uniform part. It is possible to take
In order to evaluate the thermal properties, the spray dried powders
advantage of the traditional porcelain industry materials by adequate
and PlotPaste 1 were characterized by differential thermal analysis
the pseudoplastic behaviour of its pastes with additives, improve wall
(DTA) and thermogravimetric analysis (TG) in a Seteram Labsys DTA/
stability and shape retention by using high solid content and/or by
TG equipment and dilatometry analysis (DA) using a powder pressed
solvent evaporation. The aluminosilicates based pastes have a natural
sample in a Linseis, Adidi 4.0 equipment.
adhesion behaviour that improves R3D layer adhesion and plasticity,
A rheological study was conducted to identify suitable PlotPastes for
beneficial for a successful print.
R3D. The pastes were prepared from the same mixing batch, using the
However, in order to obtain accurate parts with surface finish con­
same preparation times. The effect of H2SO4 in rheological properties of
trol, it is necessary to study the formulations and to optimize the
PlotPastes was evaluated by a rheological study using a cone - plate
properties to be able to process by R3D technology [11,21,32–34].
rheometer (Kinexus lab+, Malvern Instruments) with a diameter of 40
Comparing to other material extrusion techniques (e.g. Fused Fila­
mm and a distance of 1 mm. The analysis were made at 23 ◦ C with shear
ment Fabrication (FFF)), R3D does not require polymerization or so­
rate of 0.1–500 s− 1 and quantitative examination was assessed through
lidification reactions of a melted polymer to reach the solid state. To
rSpace software. The pH of each PlotPastes formulation was measured to
keep the structural integrity while constructing a 3D model, R3D focuses
complement the rheological analysis.
primarily on the rheological features of the deposited material and on
Some models have been reported in the literature to describe vis­
the drying of the individual layers. To control the suspension rheology
cosity behaviour and predict printing conditions [27,31,36–38]. The
it’s essential to consider the following parameters [35]: particle con­
Ostwald-de Waele power law expresses the relationship between the
centration, particle size and particle size distribution, particle
shear stress (τ) and shear rate (Ẏ) [36] as in Eq. (1):
morphology and particle-particle and particle medium interactions. In
porcelain, powders particle size and morphology are normally deter­ Eq. 1
n
τ = kẎ
mined by spray drying industrial production and thus fixed. The particle
concentration in the suspension medium and the pH values can help to where k is the flow consistency parameter and n the flow behaviour
adjust the viscosity of pastes for R3D. The colloidal interactions can help index. The viscosity (ⴄ) depends of shear rate and can be defined from
to understand the effect of pH and composition on the viscosity of pastes. the following equation [36]:
The present study aimed to evaluate the feasibility of using AM
Eq. 2
n− 1
technologies, particularly R3D with industrial porcelain powders. ⴄ = kẎ
Different porcelain formulations were studied and the respective rheo­ The combination of expressions provides the relationship among τ, ⴄ
logical behaviour evaluated in order to determine the adequate prop­ and Ẏ as follows [36]:
erties to manufacture porcelain by R3D. This study showed the potential [ n− 1 ]
of working this material in a free shape control system and opens up τ = kẎ Ẏ = ⴄẎ Eq. 3
countless possibilities for mass customization in the tableware field. This
According to the flow behaviour index value, the flow can be clas­
paper was also focused on study of operational printing conditions in
sified as Newtonian (n = 1) or Non-Newtonian (n∕ =1), being in this case
R3D technology.
pseudoplastic - shear thinning (0 < n < 1) or dilatant – shear thickening
(n > 1). Some materials flow only from the yield stress (τy) value. The
2. Materials and methods
Herschel-Buckley model was used to describe this nonlinear flow
behaviour by Eq. (4) [27,36,39–41]:
2.1. Preparation of porcelain formulations
τ = τy + k.(Ẏ)n Eq. 4
Spray dried industrial porcelain powder from a Portuguese company
(Porcelanas da Costa Verde S.A.) and a deflocculant, carbonic acid-based where τy is the yield stress.
polyelectrolyte (DOLAPIX CE 64), were used. The thickening agent The effect of rest time on the PlotPastes with the highest viscosity
applied was a solution of sulfuric acid (9.8 wt%) from Sigma. Seven was also analysed using the previous procedure. The fresh PlotPastes
formulations (designated by PlotPastes) were prepared to be processed (rest time 0 h) were compared with PlotPastes maturated with rest times
by R3D technique (Table 1). Porcelain powder was mixed in a ball mill of 24 h and 48 h. The study of the particles surface electrical charge was
(Fritsch Pulverisette 6), at 300 rpm, during 4 h, with the deflocculant in also carried out in a zeta potential equipment (Zetasizer Nano ZS,
a distilled water (H2O) media and other PlotPastes composition Malvern) using electrophoretic light scattering method. The

2
L.S.O. Pires et al.
measurements covered the range of 0.38 nm–100 μm and a minimum of
20 μl was used as sample volume. Zeta potential was analysed as a
function of pH, measured with a pH meter (Mettler Toledo™, FiveGO pH
F2).
2.3. Additive manufacturing by robocasting and characterization of
printed parts
The seven PlotPastes formulations were tested in a plotter (3D-Bio­
plotter®Developer Series – EnvisionTEC) to assess its flowability. Mass
flow rate was determined by measuring the mass deposited in 1 s at the
pressures of 1, 2, 3, 4 and 5 bar, using a noozle with a diameter of 0.41
mm. The PlotPaste with highest viscosity and lowest flow rate was
selected for AM of samples by R3D technique.
3D virtual models were designed using computer-aided design (CAD)
software (SolidWorks®) and the Visual Machines software. The models
were fabricated in plotter with controlled parameters defined in Visual
Machines software. A honeycomb part was designed and fabricated with
(30 × 30 × 5 mm3) (Fig. 1). In order to achieve reproducible accuracy
and stable extruded filaments and printed layers, different parameters
were studied and controlled: i) pressure, ii) speed and iii) layer height
(offset).
Syringes with 30 cm3 were filled with the PlotPastes and tested, at
room temperature with the R3D plotter. The printability tests were
performed using a 0.41 mm nozzle and layer height (offset) of 0.32 mm
at print two speeds (5 and 10 mm s− 1) and several dispensing pressure
(1, 1.5, 2, 2.5, 3 and 3.5 bar). A linear layer was printed with those
operating parameters, and the suitable parameters for print honeycomb
part model were selected. The morphological characteristics of extruded
filament and printed first layer were analysed by SEM.
After printing, the top surface of R3D porcelain parts were photo­
graphed (Reflex Canon EOS 100D). Those images were treated using
Gimp 2.10 software to ensure a good contrast. The total surface area was
measured imageJ 1.51j8 software. The results of those measurements
were compared with the theoretical area obtained from the CAD model
(263.68 mm2):
Af − A0
%Dimensional Deviation = • 100 Eq. 5
A0
where A0 is the theoretical area obtained from the CAD model and A0 is
the area of printed part.
The printed parts were dried at 70 ◦ C for 24 h in a vacuum oven
(Carbolite AX60 model) to remove the moisture content. After dried the
samples were sintered through time-temperature programs supported
by a thermal study previously carried out by DA and DTA/TGA analysis.
For characterization of porcelain samples, the printed parts were
sintered in two different step conventional heat treatment in air and
cooled to room temperature: i) first firing - the samples sintered at
950 ◦ C for 2 h and ii) second firing - completely sintered samples at
Fig. 1. Honeycomb part CAD model (wall width: 0.4 mm).
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1350 ◦ C for 2 h.
Morphological characteristics of surface and fracture surface of non-
sintered samples and completely sintered samples were observed by
SEM. Crystalline structure was confirmed by X-ray diffraction (XRD) in a
Rigaku Geigerflex DMax-C X-ray diffractometer with CuKα radiation.
3. Results and discussion
3.1. Materials characterization
3.1.1. Microstructural properties
R3D technique involves the extrusion of pastes through nozzles with
specific size. Lower diameter nozzles usually promote the extrusion of
lower height printed layer and consequently an improvement of the
surface roughness. The study of the particle size and morphology is thus
very important to enable the identification of nozzles diameters limi­
tations. The industrial porcelain spray dried powder (Fig. 2) is composed
of quasi-spherical particle agglomerates with 142 ± 63 μm medium size
and the characteristic punch hole from the spray drying process. The
agglomerates are in fact composed of irregular and flat shape particles
with sizes varying between 3 and 15 μm. The sub-micron features can be
only observed at higher magnifications. The preparation of the Plot­
Pastes was made in a ball mill to achieve an adequate dispersion and
homogenization of mixture constituents. The wet ball milling at 300 rpm
was enough to desegregate the spray dried spherical agglomerates
resulting in separate particles with average sizes less than 100 μm. This
procedure allows better flowability of particles in nozzles diameters
greater than 0.41 mm (minimum nozzle size used) resulting in a stable
extruded filament. Although the literature recommend the use of nozzles
with diameter higher than 0.5 mm to prevent nozzle clogging, some
authors demonstrated that it is possible to use nozzles lower than 0.5
mm with ceramic particles with a maximum diameter of 128 μm [42,
43]. The PlotPastes should have particles with a maximum diameter
smaller than one half of nozzle size used [43]. It’ is necessary to control
the particle size and not use large particles that could block the paste
flow.
3.1.2. Thermal properties
The thermal behaviours of the PlotPastes and of the spray dried
powder is very similar. From the DA curve (Fig. 3a) the PlotPaste 1
shrinks almost 14% while the shrinkage of the powder is near 11%. Also,
it can be observed, around 575 ◦ C a small expansion due to quartz α to β
transformation that is followed by a small shrinkage at about 1000 ◦ C
due to the formation of a glass phase [44–46]. After 1000 ◦ C the sin­
tering process begins, followed by high shrinkage and subsequent
Fig. 2. SEM images of spray dried porcelain powder at 40x, 1000x and 5000x
magnifications.
L.S.O. Pires et al.
Fig. 3. Thermal behaviour of spray dried powder and PlotPaste 1: a) DA b) DTA
and TG.
densification. DTA and TGA (Fig. 3b) also show similar trends typical of
porcelain sintering behaviour. In the DTA curves it is possible to
observe, in both spray dried powder and PlotPaste, an endothermic peak
at around 100 ◦ C due to the loss of adsorbed water. The endothermic
peak observed at 543 ◦ C is attributed to the release of structural water
from the clays crystalline structure and organic components burnout and
also the α → β quartz transformation. The exothermic peak at 1000 ◦ C is
ascribed to mullite phase formation [47,48]. The final weight loss is
about 6.5% for the spray dried powder and 7.8% for the PlotPaste 1,
which reflects the observed difference in hydration levels and water loss.
A similar behaviour was observed in porcelain thermal studies reported
in literature [44–48].
3.1.3. Rheological properties
The ceramic suspension rheology was already studied in order to
stabilize the ceramic particles and obtain a homogenous suspension.
Additives are normally used in ceramic industry to obtain low viscosity
suspensions (e.g. slip casting suspension; viscosity around 2000 mPa s at
10 s− 1) with high solids content but in the present study it is necessary to
increase the viscosity in order to acquire material extrudable capacities
[49–51]. The rheological behaviour of the PlotPastes was consistent
with what was found in other studies [13,51–59]. The acidic modifica­
tion of the different formulations didn’t change the rheological trend
behaviour of the PlotPastes. In fact, all pastes show a typical
non-Newtonian or shear thinning viscosity behaviour - pseudoplastic
(Fig. 4a), confirmed by the decrease of apparent viscosity with
increasing shear rate. During the manufacturing, as the pseudoplastic
transition to dilatant is time dependent, the deposition rate should be
controlled. If the drying rate is too slow, the pseudoplastic to dilatant
transition is delayed and the cumulative weight of the different printed
layers will exceed the yield stress of the pseudoplastic behaviour pro­
moting no uniform walls. On the other hand, if the drying speed is too
fast, plastic deformation may occur, namely cracks in each printed layer
[13,25,26,42,60].
For the same shear rate low viscosity pastes allows higher material
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Ceramics International xxx (xxxx) xxx
Fig. 4. Rheology measurements of the PlotPastes: a) shear rate/apparent vis­
cosity and b) pH/apparent viscosity.
deposition that leads to higher width of printed filament. After printing,
if the paste doesn’t have enough stiffness, the printed wall cannot sup­
port itself and may crumble under its own weight. For that reason, it is
reasonable to choose a paste that presents low viscosity at higher shear
rate (in this study around 10 -15 s− 1) for suitable extrudability, but after
deposition, it shows an increase of viscosity associated with thinning
behaviour, as the paste recuperates the initial behaviour at shear rate
0 s− 1.
Fig. 4a shows how a small decrease in the pH level of the stock so­
lution increased the apparent viscosity of the PlotPastes. Namely
changing the pH from 7.04 to 1.94, by addition of H2SO4 9.6% aqueous
solution, the initial viscosity increases by nearly 10 times. These changes
with increasing acid content could be observed during the mixing, as the
consistency of the mixture shifted from aqua like texture to a smooth
creamy paste. This behaviour is related with changes in the particles
surface that modifies the interaction of each other. The increase of the
surface charge of the ceramic particles (related with low pH), promoted
particles agglutination/flocculation resulting in a more viscous and
stable extrudable paste.
Different deflocculates showed different effects on viscosity [57,61].
In case of Dolapix, no significant effects were observed on PlotPastes
compositions. Tsetsekou et al. [53] also observed low effects of Dopalix
in the viscosity of alumina slurry (80 wt % solids content) for concen­
trations of 0.3–0.4 wt %. Ordoñez et al. [57] analysed the effect of two
different deflocculants (sodium silicate and sodium polyacrylate) and
showed that sodium polyacrylate had more significant deflocculant ef­
fect on the viscosity of a traditional clay paste. Adding low concentration
of sodium polyacrylate decreases the paste viscosity and allows the
extrusion of pastes with higher solids content (53 vol%). In our study,
there is a point after which the initial viscosity diminishes to values
about two-fold of the initial (PlotPaste 6 compared to PlotPaste 1) with
L.S.O. Pires et al.
increasing addition of acid content. There is a limit to which the effect of
pH is overshadowed by the water lubrication effect in the clay particles
surface, a behaviour clearly identified for pH lower than 1.94. Viscous
pastes in R3D technique have high potential to yield good results in
terms of structural integrity and printed layers stability. After filament
deposition, pastes of higher viscosity have higher support capacity
resulting in higher shape fidelity with increasing printed height [57].
There is a pH region (Fig. 4b) in which the viscosity increases for each
shear rate. In fact, higher viscosity can be attained for pH levels lower
that 3.4 even at 10 s− 1. At 100 s− 1 all pastes have nearly 0 Pa s viscosity
levels. PlotPastes 5 and 4 showed the highest viscosity values for all
shear rates. The viscosity of PlotPastes tend to be higher with increase of
sulfuric acid content and consequently decrease of pH. However, the
PlotPastes 6 and 7 didn’t follow this behaviour. These PlotPastes present
lower viscosity because its water content discontinued the agglomera­
tion effect, promoting higher lubrication and particles flow. Similarly,
Carty et al. [35] also promoted an increase in viscosity of alumina sus­
pensions by adjusting the pH through addition of H2SO4 and HCl. Other
researchers [51], used an acrylic binder, in alternative of polyvinyl
alcohol (PVA) - one of the most common used binder in industry, and the
viscosity of clay suspensions (40 vol% solid) increased as the binder
content (until 8 wt%) increased.
According to the graph in Fig. 4a, the candidate pastes to be printed
are those that comply with the agreement of lowest viscosity at high
shear rate (for extrusion the filament) and high viscosity after depos­
iting. For extrudability, all pastes are suitable, however some of them (e.
g: PlotPaste 1, 2 and 3) can’t retain the shape after deposition (shear rate
0s− 1). Regarding to that, the viscosity of the paste is intended to be
higher (than during the extrusion), so that the filament retains the
printing shape. The highest viscosity paste for shear rate 0s− 1 is Plot­
Paste 5, showing the highest recovery.
According to the Herschel-Buckley model, the rheological fit pa­
rameters (Table 2) confirm the shear-thinning behaviour with n value
smaller than 1. It is observed that k parameter increases as viscosity
increases until PlotPaste 5 in accordance with the previous rheological
results. These results are in agreement with other studies with ceramic
pastes [9,54,62–68].
The viscosity was not only affected by the composition (e.g. acid
content) but also by the rest time (Fig. 5a). After 24 h and 48 h of rest
time, the PlotPaste 5 presented higher viscosities compared to the fresh
paste. Evaporation water and organics diffusion during the paste
maturation time increased the viscosity. In addition, the occurrence of
particles sedimentation and the entanglement of organic chains strongly
contributes to increase the resistance to the shear rate. It is reported in
literature [43,49,69,70] that viscosity usually increases with the in­
crease of solid contents in ceramic suspensions. Increasing the PlotPastes
rest time, the concentration of solids increase (the water content
decrease). As a consequence the freedom of particles movements
diminished and consequently an increase of flow resistance is observed
[32].
The stability of R3D formulations can be controlled by shifting the
attractive and repulsive forces of the particles – interparticle van der
Waals forces, which can induce flocculation by agglomeration/coagu­
lation of particles. Some dispersants (e.g. polyelectrolytes, carboxy­
methylcellulose (CMC)) have been used in order to maximize the
Table 2
Herchel-Bulkley equation curve fitting parameters of PlotPastes.
PlotPaste n k (Pa.sn) R2
1 0.23 21.67 0.99
2 0.20 38.23 1.00
3 0.33 65.44 0.98
4 0.37 239.44 0.99
5 0.28 295.45 0.99
6 0.42 153.90 0.98
7 0.50 75.27 0.98
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Ceramics International xxx (xxxx) xxx
dispersion forces for ceramic suspensions with high solids content [8,9,
70]. Promoting particle separation during the milling process, improves
the homogeneity of paste mixture for improved extrusion properties,
higher viscosity and better wall stability, that can be attained with
adjusting the agglomeration state. pH measurements have been carried
out to adjust the dispersant effect on the repulsion/agglomeration of
suspended ceramic particles. Some additives allow adjusting the pH of
the suspensions and consequently affect the rheological behaviour [71,
72].
Through zeta potential analysis (Fig. 5b) it was possible to estimate
the state of particles aggregation and mobility as a function of electrical
charge. When the particles have the same charge due to the electrostatic
forces, they repel each other, reflecting it in a total charge other than
zero. When total charge is closer to zero (attraction of the particles) the
particles mobility decreases while the paste viscosity increases. On the
other hand, if repulsion increases, the mobility increases and promotes
lower viscosity. Typically, the surface charge of clays and clays-based
materials changes with pH. In clays, there is a tendency of zeta poten­
tial increases with decreasing pH (− 30 to − 13 mV for kaolinite) [73].
Fig. 5b shows de evolution of charge on particle surface of PlotPastes
with variation of pH. For higher pH, due to the decrease of electric
potential at the particles surface, there is an increase of the repulsion
force which promotes higher particle mobility. So, it is possible to
change the rheological behaviour controlling the pH of PlotPastes. In
case of zeta potential of PlotPastes with rest time, no significant changes
were observed in acid medium. Zeta potential analysis suggests that
resting time increases the viscosity above ±15 mV. A similar trend was
obtained in the case of fresh PlotPaste 5 for pH less than 2.5. According
to the rheological results (Figs. 4b and 5a), the viscosity of PlotPaste 5
decreases with the increase of pH, primarily for pH greater than 3. The
same trend was observed for the PlotPaste 1 but with considerable lower
viscosity compared to the PlotPastes. The effect of pH and individual
raw material on rheology behaviour was already studied [50,74]. For
example, Zhang et al. [74] showed that Al2O3/SiC suspensions pre­
sented lower viscosity compared to individual suspensions of Al2O3 and
SiC. Al2O3 and SiC particles had opposite surface charges (at pH = 3–6)
and consequently different rheology results. The controlled use of ad­
ditives allows to adjust the zeta potential of pastes and achieve print­
ability. It was also demonstrated that the addition of an electrolyte (i.e.
NaCl) increases the apparent viscosity due to the increase of concen­
tration of the counter ions that promote an increase of inter-particle
network strengthening. Ben-Arfa et al. [75] reported that negative
charges of CMC on glass suspension promotes a decrease of zeta po­
tential with increasing pH, acting as dispersant agent especially for pH
around 10. Glass suspensions with higher solid content and higher
concentrated of CMC promoted an increase of viscosity due to the in­
crease of solids content and consequent entanglement of the long CMC
chains. In case of PloPastes, the H2SO4 was the main responsible com­
pound for the significant surface charge modification and increasing
viscosity of PlotPaste (Fig. 5 a).
In fact, the pastes with higher viscosity are more suitable to retain the
shape after printing. According to the rheological tests (Fig. 5 a), the
pastes with rest time (24 h and 48 h) should have better shape fidelity
than the fresh paste (rest time 0 h). However, the rest time allows
diffusion and aggregation of the particles which difficult the printing
step, showing higher propensity for thinner nozzle clogging. This
behaviour is according to the zeta potential results that showed more
aggregation propensity of the pastes with increasing rest time for all pH
values.
3.2. Robocasting and characterization of printed parts
According to previous results, regarding to the R3D tests fresh
PlotPastes 2.5 were used for reliable printing tests.
In order to evaluate the mass flow rate (ṁ) corresponding to the
pressure (P) controlled by the R3D equipment, the relationship between
L.S.O. Pires et al. Ceramics International xxx (xxxx) xxx

Fig. 5. Rheology measurements of fresh PlotPastes and after rest time (24 and 48 h) (a) and Zeta Potential results (b).

both variables was plotted for each PlotPaste. Fig. 6 shows a dependence be determined by the following interpolated equation (Fig. 6):
of mass flow rate with paste viscosity (Fig. 4a). The mass flow rate de­
ṁ = 0.0026P2 + 0.023P − 0.045 Eq. 6
creases with decreasing pH until 1.94 pH of PlotPaste 5 – the more
viscous paste. The increase of mass flow rate for PlotPaste 6 and 7 is The apparent shear rate (Ẏapp) of PlotPaste 5 during extrusion in R3D
associated to the lower viscosity of these pastes due to increase of acid was estimated by the following equation [76]:
aqueous solution as previously discussed. The PlotPaste 5 shows the
4Q
highest viscosity and lowest flow rate compared to other PlotPastes. This Ẏaap = Eq. 7
PlotPaste was selected for R3D tests. The mass flow rate of PlotPast 5 can
π r3

where Q is volumetric flow rate in R3D calculated from the mass flow
rate and density of PlotPast 5 (1.63 g cm− 3) and r is the radius of nozzle.
Table 3 shows that the Ẏapp increases with increase of dispensing pres­
sure and consequent higher volumetric flow rate of PlotPaste 5. The
maximum shear rate of 32.09 s− 1 is applied with higher pressure of 3.5
bar when the PlotPaste 5 is extruded through the nozzle of 0.41 mm.
This behaviour was observed in other R3D studies with ceramic pastes
[65,77].
A digital model of honeycomb structure was developed. To obtain a
thin part it was used a nozzle with small diameter (0.41 mm). In order to
select the adequate operating parameters to the PlotPaste 5, individual
linear layers with 0.32 mm layer height were printed with different

Table 3
Ẏapp for each dispensing pressure in R3D of PlotPaste 5.
Pressure (Pa) 1 1.5 2 2.5 3 3.5
Fig. 6. Relation between mass flow rate and pressure (R2 = 1 for all Plot­ − 1
Ẏmax (s ) 0.36 0.03 9.52 15.87 23.39 32.09
Pastes curves).

6
L.S.O. Pires et al.
pressures and speeds (Table 4). This methodology of first printing a
linear layer to analyze the print conditions is reported in the literature
for other studies [27,78–81]. The results are in agreement with the
previous indications of mass flow rate vs pressure results (Fig. 6). Mass
flow rates near to 0 g s− 1 occur with pressures bellow 2 bar which
prevents the extrusion of a continuous linear layer. There is a tendency
of increasing the linear layer width with the increase of pressure. On the
other hand, the increase of speed for a certain pressure allows the
decrease of linear layer width. Habib et al. [82] also showed the same
effect of pressure on linear layer of a formulation composed of alginate,
CMC and montmorillonite clay. In their study, lower pressures and a
nozzle of 0.41 mm promoted a discontinuous linear layer and the author
attributed to the surface tension of the extruded material not exceeded.
As stated in the literature, smaller nozzle diameter (as 0.4 mm) usually
require higher print pressure-speed ratio to print a stable linear layer
[43]. Table 4 showed that low speeds and high pressures tend to pro­
mote the swell die behaviour - stress relaxation in material that occurs
laterally to the nozzle favoring a U-type cutting effect by the proximity
of the extrusion nozzle to the build platform (offset 0.32 mm). Associ­
ated to the shear thinning behaviour, it’s verified the ability to extrude a
continuous and uniform filament into air on Fig. 7 a [27]. SEM micro­
graphs showed morphological differences between a linear layer with a
swell die effect (Fig. 7 c) and one printed under appropriate conditions
(Fig. 7 b). The quality of linear layer is affected and results in a smaller
expected width relative to the volume of material deposited (e.g. linear
layer 5 mm s− 1 of speed and 3 bar of pressure compared with 5 mm s− 1
of speed and 2.5 bar of pressure). A dimensional difference (greater than
double) was also observed between the extruded filament (without
contact with the build platform) and the linear layer printed on the
platform with an offset of 0.32 mm. There is a plastic deformation in the
filament deposition that allows to stabilization of the construction and
create adhesion between added layers. Based on the linear layer tests,
key input parameters have been identified (speed of 10 mm s− 1 and
pressure of 2–2.5 bar). The effect of printing pressure, printing speed
and nozzle offset on stability of printed linear layers is complex and to
some extent already reported [27]. Generally, pastes with higher vis­
cosity shows more shape fidelity but each one of the composites pastes
requires proper parameters control such as increased pressure to extrude
the filament.
Different combinations of pressure and speed were tested to manu­
facture a honeycomb part. The model printed with lower pressure and
speed showed a very thin and brittle width wall (Table 5 (a)). Small
increase of pressure values promote an increase of model wall width and
resistance (Table 5 (a) compared to Table 5 (b)). Higher pressure
consequently increases the mass flow rate increasing the width of each
one of the printed layers (Table 5 (b) compared to Table 5 (a)) pro­
moting more stability to the 3D construction. The adjustment of
Table 4
Study of the effect of R3D operating parameters (figures scale: 10 mm ( )).
7
Ceramics International xxx (xxxx) xxx
operating process parameters provided more balanced dimensions and
strength for the model (Table 5 (c)). After testing the honeycomb
structure, the manufacture of the contour was also tested.
The printed models show a projected area different from the one
obtained from the CAD model (263.68 mm2) (Fig. 8). This difference
result from a combination of printing conditions (layer height, printing
speed, pressure and nozzle diameter) that reflect the filament spread.
There was an increase of 15.78% and an increase of 101.02% in the
printed filament width for pressures 2 and 2.5 bar, respectively. The
printing pressure has a direct influence on the width of the printed parts:
a pressure increase originates larger filaments, that enables the con­
struction of higher builds. The deposition strategy is another factor that
influences the printed filament width. In the present work, the honey­
comb pattern is obtained by a zigzag route that overlap the joints of half
hexagons (Fig. 8 (a)). This printing strategy thickens the deposited
filament in the joints, which locally increases the filament width of
honeycomb (Fig. 8 (b,c)). With higher pressure, there is a synergy effect
with the joints overlap, that explains the variability of the printed fila­
ment width, regarding the width of the theoretical CAD model (Fig. 8 (c,
d)). It’s possible to improve the printing fidelity by adjusting other
printing conditions, such as increasing printing speed or increase the
layer height, that result in a decrease of layer width [27,43,79,80,82].
After observing the printed models in SEM, some challenges related
with optimization of geometry were yet identified. Although Fig. 9
showed a good adhesion in stacking between successive green layers, it
also showed evidence of closed porosity before and after heat treatment.
It was also observed a decrease of the stacked layers width regarding the
first layer due to the weight of the overlapping layers and the paste
consistency. The vertical abatement due to layers overlapping and
structure weight was also reported in other studies of R3D of ceramics
[62,63,75,83]. These dimensional deviations changed the filament
normal shape from circular at the tip of the nozzle to elliptical during
printing [63,75]. Similar results were reported [27,84] on printed layer
relaxation onto the underlying layers that promoted non uniformity of
wall. There is evidence that using high molecular weight polymer on
boron carbide pastes promotes an increase of viscosity and higher
strength to support additional deposited layers which reduces the
overlapping effect [63]. The increase of solids content improved the
shape retention, but high solids contents (>55 vol %) promoted
clumping, nonuniformity layer due to the drying of paste and build-up in
the nozzle, as well as warpage due to anisotropic shrinkage [29,63,77].
In case of Fig. 9 (a), there was a plastic deformation more evident on first
layers. The final stabilization is only achieved by heat treatment after
printed models. Until then, it is necessary to optimize process parame­
ters to manufacture parts with a geometry and dimensions closer to the
projected digital model. In this case study, the constant dimensions were
more difficult to achieve by the required thin walls. There was also some
L.S.O. Pires et al.
Fig. 7. SEM micrographs of extruded filament into air (a), printed linear layer
on build platform (b) and printed linear layer on build platform with U-type
effect (c).
difficulty in obtaining sharp corners. Fig. 9 (b) also shows an increase
mass deposition on corner through the decrease of speed that occurs
while changing direction. The printed layer dimensions are primarily
defined by process parameters such as printing speed, flow rate e nozzle
diameter, that are adjusted to each print. It’s possible to compensate
8
Ceramics International xxx (xxxx) xxx
Table 5
Operating process parameters to manufacturing 3D model: sintered honeycomb
structures (a, b) and green honeycomb model with contour (c,d).
Speed (mm/s)
Pressure (bar) 10
2.5
Fig. 8. Dimensional deviation measurement of R3D porcelain honeycomb: (a)
theoretical area obtained with zigzag printing strategy. Green porcelain R3D
parts printed with 2 bar (b) and 2.5 bar (c). Overlapping of green porcelain R3D
parts with CAD theoretical model (d, e).
such deviations with new approaches that stabilize the printed layer
after extrusion and improves the material viscosity and stiffness (e.g.
post printing light cross-linking photosensitive additives) [27,84].
Aiming to obtain an uniform partial drying, Ghazanfari et al. [85] used
an oil surrounding medium (heated by IR radiation) to ensure wall
L.S.O. Pires et al. Ceramics International xxx (xxxx) xxx

stability on R3D of printed alumina layers. Mohammadi et al. [60]

decreased the drying speed controlling the humidity inside the printer
through an ultrasonic humidifier. These approaches allowed to keep the
layer shape and prevent cracks or warpage. The use of adaptative pa­
rameters control system during the printing process have been also
discussed in literature to avoid some of these problems [27,85]. In real
time adjustments of printing speed and pressure can ensure the print
fidelity by controlling the thickness of the deposited layer.

4. Conclusion

Pastes for R3D were formulated based on industrial porcelain spray

dried powder with a deflocculant and a solution of sulfuric acid. The
study of particle size and morphology allowed to identity the minimum
possible nozzle diameter (0.41 mm) to be used in an AM material
extrusion process - R3D. Through a rheological study it was possible to
prepare and identify a porcelain paste with adequate properties to be
processed. The PlotPastes formulated exhibit shear thinning behaviour
(pseudoplastic). Different contents of H2SO4 9.6% solution changes the
pH affecting the viscosity. The decrease of pH increases the surface
charge of ceramic particles promoting the attraction among them and,
consequently, increasing the viscosity. The PlotPaste 5 (pH 1.94) pre­
sented the higher value of viscosity among all the other PlotPastes. The
rest time also affected the viscosity increasing the resistance to the shear
rate compared to fresh paste.
The R3D technique was tested as a versatile alternative method to
manufacture customized porcelain products with very thin and complex
geometries that are difficult or impossible to obtain by conventional
industrial methods. Regarding to R3D parameters, an increase of pres­
sure and a decrease in speed promotes a larger linear layer width. Bellow
2 bar was not possible to extrude a continuous filament. High pressures
tend to promote defects on filaments due to a high mass flow rate. It is
possible to control the printability of the honeycomb 3D model, namely
the thickness of the wall. It was also evident the influence of operating
process parameters on dimensional accuracy. Minor parameter changes
may compromise the stability and geometry of thin walls. In this work,
robust honeycomb parts were produced, although higher wall stability
implies higher dimensional deviation, due to the higher pressure used in
the R3D process. There are studies being conducted to assess the effect of
specific printing parameters on different model shapes, on the printed
material properties and its relevance on the customization of ceramic
products.

Declaration of competing interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence
the work reported in this paper.

Acknowledgments

The authors are greatly acknowledging the efforts endorsed by Por­

celanas Costa Verde, SA and their valuable R&D contribution in this
project.
This work was developed within the scope of the RoboCer3D project
– project of additive rapid manufacturing through 3D printing ceramic
material, POCI-01-0247-FEDER-003350, financed by Fundo Europeu de
Desenvolvimento regional (FEDER), through Programa Operacional da
Competitividade e Internacionalização (POCI - COMPETE 2020).
This work was also developed within the scope of the project
CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/
2020 & LA/P/0006/2020, financed by national funds through the FCT/
MCTES (PIDDAC).
Fig. 9. SEM micrographs on top surface and fracture of green (a, b) and sin­
tered (c,d) model manufactured with 2.5 bar and 10 mm s− 1.

9
L.S.O. Pires et al. Ceramics International xxx (xxxx) xxx

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