Internal

Chapter 3: Materials and methods

This chapter delineates the materials and methods employed in the fabrication and
characterization of functionally graded porous zirconia. The contents of this chapter
are organized into sections, covering material selection and ink preparation, the
fabrication process, and materials characterization techniques. The flowchart
presented in Figure 1 outlines the activities conducted in this section throughout the
course of this thesis.

Figure 1:Process Overview Flowchart

3.1 Ink Preparation and characterization:

3.1.1 Materials:
The list of materials used to produce the ink for DIW have been given in Table 1.

Table 1:Materials used to produce ink for DIW

Ceramic CEZ-12

Sacrificial fugitive Corn starch, Potato starch

Carrier Water
 Internal

Binder Pluronic® F-127

Dispersant Dolapix 64 CE

The ceramic powder utilized was CEZ-12 (CeOx)x(ZrO2)1-x, a commercially available

16 wt.% Ceria stabilized Zirconia powder from Daiichi Kigenso Kagaku Kogyo co.,
ltd., Osaka, Japan. Its composition and properties are detailed in Table 2 and Table
3.

Table 2:Chemical composition of CEZ-12 [1]

ZrO2 + HfO2 (wt%) CeO2 (wt%) Al2O3 (wt%) SiO2 (wt%)

83.71 16.29 0.26 0.003

CEZ -12
Fe2O3 (wt%) TiO2 (wt%) Na2O (wt%) CaO (wt%)

0.001 0.002 0.001 0.001

Table 3:Properties of CEZ-12 powder and sintered ceramic as report by Daiichi [1,2]

Property Unit Value

Loss on Ignition (H2O containing) wt% 0.56

Average Particle size µm 0.72

Specific surface area () m2/g 11.5

Green density - 1.0t/cm2 () g/cm3 2.87

Sintered density - 1.0t/cm2 (g/cm3) g/cm3 6.21

Given data is for molding using Cold Isostatic Pressing and Sintering at 1450°C

In the course of this research, two distinct varieties of starch, namely corn starch and
potato starch, were employed as sacrificial fugitives. The corn starch utilized in the
experiments was sourced from Sigma Aldrich. On the other hand, the potato starch
utilized in the study was obtained from Maizena, a brand which sells food products.
The average particle size and the density of the starches used have been given in
Table 4. SEM pictures of the two types of starch used have been shown in Figure 2.

Table 4:Properties of starch used [3]

Company Density Particle size Loss on pH

(g/cm3) (µm) Drying
(2% in H2O)

Corn Starch Sigma 1.34 10 - 20 < 15.0% 4.0 – 7.0

 Internal

aldrich

Potato Maizena 1.22 30 - 100 - -

Starch

( - ) product information not provided by manufacturer

(a) (b)

Figure 2:Corn starch (a) and Potato starch (b)

The carrier employed to achieve the desired rheological parameters consisted of a

mixture of Pluronic® F-127, henceforth denoted as PF-127, with deionized water (DI
water) and the dispersant Dolapic 64 CE. PF-127, a non-ionic triblock copolymer
represented by the chemical formula (C3H6O·C2H4O)x, was procured from Sigma
Aldrich, and its properties are detailed in Table 5. The organic flocculating agent
Dolapix 64 CE, sourced from Zschimmer & Schwarz, is detailed with its properties
presented in Table 6.

Table 5:Properties of Pluronic® F-127 [4]

Linear Formula (C3H6O·C2H4O)x

Appearance (Color) White

Appearance (Form) Powder

Solubility (Color) Colorless

Solubility (Turbidity) Clear

PH of Solution (PH) - 2.5 % Solution 6.0 - 7.0

Formula Weight 8.400 g/mol

Water ≤ 0.75 %

Table 6:Properties of Dolapix 64 CE [5]

Property Unit Value

 Internal

Appearance (colour) - Yellowish viscous solution

Active matter % ~65%

Solublity - Water-soluble

Density (20°C) g/cm3 1.2

pH - 7

Molecular weight g/mol 660

3.1.2 Ink preparation:

The initial step in ink preparation involved the preparation of the pluronic solution,
serving as the carrier. This solution was prepared by combining 25g of PF-127
powder with 75g of DI water. Subsequently, the mixture underwent homogenization
in a turbula mixer (3D Shaker Mixer Turbula, WAB) for 72 hours to achieve
uniformity.

The ink formulation process involved two distinct protocols. In both protocols, the
carrier was PF-127 solution and zirconia milling balls were the chosen milling media.
The weight of the milling balls equating to the combined weight of the zirconia and
starch utilized in the ink. The preparation of inks occurred within 10ml-sized
containers, and subsequently, the inks were transferred into syringes for the
extraction of filaments in the DIW process. The names and the composition of the
various inks prepared in this thesis have been given in Table 7, tables and the
weights of each component of the ink have been given in Table 8 to Table 12.

Table 7:Composition of each prepared ink

Starch Zirconia
Name Starch nature
(vol%) (vol%)

10 vol.% CS Corn starch 10 30

20 vol.% CS Corn starch 20 20

30 vol% CS Corn starch 30 10

30 vol% PS Potato starch 10 30

Pure CEZ-12 - - 40

Table 8:Composition of pure CEZ-12 ink

Component vol% wt% Amount
CEZ-12, g 40 80.49 24.84
Starch, g 0 0 0.00
 Internal

Dolapix 64 CE, ml 0.5% of CEZ-12 0.10

PF127 solution, ml 19.11 5.90
Milling balls, g 24.84
Weight of ink, g 30.86

Table 9:Composition of 10 vol.% CS

Component vol% wt% Amount
CEZ-12, g 30 71.69 18.63
Starch, g 10 5.16 1.34
Dolapix 64 CE, ml 0.5% of CEZ-12 0.08
PF127 solution, ml 22.79 5.92
Milling balls, g 19.97
Weight of ink, g 25.99

Table 10:Composition of 20 vol.% CS

Component vol% wt% Amount
CEZ-12, g 20 58.53 12.42
Starch, g 20 12.70 2.68
Dolapix 64 CE, ml 0.5% of CEZ-12 0.05
PF127 solution, ml 28.18 5.95
Milling balls, g 15.10
Weight of ink, g 21.11

Table 11:Composition of 30 vol.% CS

Component vol% wt% Amount
CEZ-12, g 10 38.25 6.21
Starch, g 30 24.76 4.02
Dolapix 64 CE, ml 0.5% of CEZ-12 0.03
PF127 solution, ml 36.80 5.97
Milling balls, g 10.23
Weight of ink, g 16.24

Table 12:Composition of 10 vol.% PS

Component vol% wt% Amount
CEZ-12, g 30 72.03 18.63
Starch, g 10 4.72 1.22
Dolapix 64 CE, ml 0.5% of CEZ-12 0.08
PF127 solution, ml 22.9 5.92
Milling balls, g 19.85
Weight of ink, g 25.87
 Internal

Figure 3:Flowchart of protocol 1

In the first protocol, the carrier was formulated by combining PF-127 and the
dispersant. One-third of the overall mixture, comprising starch, ceramic powder, and
milling balls, was introduced into this carrier. Homogenization was achieved using a
planetary mixer (Hauschild, Speedmixer), with the RPM progressively increasing
from 800 to 2000 in four increments. An ice bath was applied between each mixing
step to maintain the ink's temperature below 10°C, ensuring the PF-127 remained in
a liquid state for efficient dispersion of solid particles. Following the 2000 rpm step,
another one-third of the total solid component was incorporated, and the preceding
steps were reiterated. The final one-third was added, and after thorough mixing, the
milling balls were eliminated by rotating the ink through a sieve at 2000 rpm in the
planetary mixer. Refer to Figure 3 for a visual representation of this process.

Figure 4:Flowchart of protocol 2

In the second protocol the solid components of the ink along with the dispersant
underwent dry milling prior to the addition of the carrier. Similar to the first protocol,
the dry milling was carried out in 3 stages where one third of the starch, zirconia, and
milling balls were combined with 0.5 wt.% dispersant and milled five times at 2000
rpm for 30 seconds in the planetary mixer at each stage. The dispersant was only
added in stage 1 and not in stage 2 and stage 3. Once the PF-127 solution was
added, the ink underwent homogenization at 2000 rpm for 30 seconds (12 times).
Similar to protocol one, an ice bath was utilized between each mixing step not only to
maintain PF-127's liquid state and but also prevent overheating of the plastic
container in the dry milling section. Refer to Figure 4 for a visual representation of
this process.

The second protocol was utilized for preparation of samples for the subsequent
testing phase based on the observation that samples produced with this ink exhibited
a reduced propensity for cracking during the drying process. This phenomenon was
attributed to the enhanced efficacy of the dispersant in uniformly coating all powder
particles in the second protocol, resulting in a more homogenized ink.
 Internal

Following ink preparation, the inks were loaded into syringes and subjected to 2000
rpm for 1 minute in a centrifuge (Hettich Rotina 35) to eliminate air bubbles.

3.1.3 Rheological characterization:

Rheological measurement was conducted to evaluate the printability of the inks. The
measurement was conducted with a rotating vane stress-controlled rheometer (MCR
501, Anton Parr). Rheological measurements of a mixture of starch, dispersant and
PF-127 was also done, to evaluate effect of starch on amount of dispersant required.

i)Measuring effect of starch on amount of dispersant required:

To assess the interaction between starch and dispersant, inks with varied
concentrations of both components were formulated. CEZ-12, the ceramic
component, was deliberately omitted to isolate the interaction between starch and
dispersant without interference from ceramic particles. It is crucial to note that the
dispersant quantity and the starch quantity was determined based on the expected
amount of CEZ-12 to be added during ink preparation for part printing. The list of
tested ink compositions is provided in Table 13. The vol% of starch correspondes to
the vol.% of starch in the ink with the CEZ-12; similarly the wt.% of dispersant was
calculated as if the CEZ-12 was added to the ink.

A consistent shear rate of 10 s⁻¹ was applied for 180 seconds to the inks at 21°C,
and the ink viscosity was determined from the final steady-state value.

Table 13: Composition of inks tested for effect of starch on amount of dispersant required

Amount of dispersant [wt.

Ink number Starch vol.%
% of CEZ-12]

1 0.2

2 10 0.5

3 0.7

4 0.2

5 20 0.5

6 0.7

7 30 0.2

8 30 0.5

9 30 0.7

ii)Measuring printability of ink:

As noted in Chapter Two, the printability of an ink relies on key rheological

parameters: viscosity, yield strength, and storage modulus. The ink's viscosity was
 Internal

determined through a flow sweep test, and the yield strength and storage modulus
were assessed using an amplitude sweep test.

The flow sweep test measures the change in viscosity with a change in shear rate.
Rotational shear forces ranging from 0.01 to 100 s -1 were applied to the inks, with 41
measuring points and a timeout of 4 seconds per measuring point. This test was
performed on 10 vol.% starch, 30 vol.% CEZ-12 and 20 vol.% starch, 20 vol.% CEZ-
12 ink at 10°C and room temperature (21°C).

The amplitude sweep test involves subjecting the slurry to sinusoidal stress or strain
and measuring the in-phase and out-of-phase responses to it. The yield stress of a
viscoelastic material is defined as the stress at which is the storage modulus (G’)
becomes non-linear. However, as this is hard to determine, the yield stress is taken
as the stress at which the elastic modulus (G’) and the loss modulus (G’’) crossover.
The list of amplitude sweep tests done have been given in Table 14. In this test shear
stress ranging from 5 to 5000 Pa at a frequency of 6.28 Hz was applied in 50
increments and the loss modulus and storage modulus were observed.

Table 14:List of amplitude sweep tests done

Ink composition Temperature of test

10°C

20 vol.% starch, 10 vol.% CEZ-12 14°C

21°C

10°C
10 vol.% starch, 30 vol.% CEZ-12
21°C

3.1.4 Thermogravimetric Analysis and Differential Scanning Calorimetry:

Thermogravimetric Analysis was done to track the changes in the mass of the
various inks with a change in temperature. Differential Scanning Calorimetry was
simultaneously done to measure the heat flux of various inks with a change in
temperature. The tests were done on a SDT Q600 (TA Instruments) with the
temperature changing from 10°C to 1000°C with a constant rate of 10°C/min. The
tests were done on inks composed of 40 vol% CEZ-12 and 30 vol% CEZ-12, 10 vol%
starch solid loading.

3.2 Fabrication of Functionally Graded Porous Zirconia:

3.2.1 Printing:
Printing was conducted using the 3DDiscovery Evolution bioprinter developed by
RegenHU in Switzerland which uses pressurized air to achieve the meterial flow from
the syringe to the printhead. This printer can accommodate four printheads and has
the capability to control the temperature of one printhead during printing. The printing
 Internal

patterns were designed by the BioCAD software. The part's shape, the direction of
nozzle movement (horizontal and vertical), nozzle travel speed, filament spacing,
number of printed layers, and layer orientation is controlled by this software.

Different printing parameters were tried out to determine the optimal set of
parameters which result in the least number of defects during printing. Various
combinations of nozzle travel speed, strand width, nozzle diameter, and layer height
were explored, as outlined in Table 15:Printing parameters usedTable 15. Moreover,
each layer was positioned at a 90° angle to the preceding one to guarantee
appropriate overlap in the vertical direction.

Table 15:Printing parameters used

Nozzle travel Nozzle

Strand width(mm) Layer height (mm)
speed(mm/s) diameter(mm)

10
0.23 0.23
8 0.25
0.215 0.215
6

The other controllable parameters were applied pressure, relative humidity and
temperature. To prevent clogging of the nozzle, the relative humidity was set to 98%.
Additionally, the nozzles were dipped into a vessel containing sunflower oil after
completion of each later to prevent clogging. Pressure adjustments were made on a
case-by-case basis, varying not only between different inks but also among samples
of the same ink which indicated that the inks weren’t a hundered percent
homogeneous. The optimal printing temperature was determined through rheological
analysis of the inks. When printing samples exclusively composed of a single ink
type, the ink was maintained at a temperature of 16°C, well within the gel domain of
PF-127. This ensured the necessary shear-thinning behavior crucial for precise
printing. The diemensions and diagram of the samples printed have been shown in
Table 8.

Table 16:Dimensions and diagram of samples printed

 Internal

10 mm x 10 mm x 2.53 mm 10 mm x 2.53 mm

In the production of functionally graded samples, a cuboid shape was achieved by

alternating two layers of pure CEZ-12 ink and either 10 vol% CS ink or 10 vol% PS
ink as shown in Figure 5. Due to the machine's limitation in controlling the
temperature of more than one syringe, only the syringe containing the pure CEZ-12
ink underwent temperature control and was held at 14°C. The second syringe,
containing the starch-infused ink, was printed immdiately after taking it out of the
refridegerator i.e, without temperature control. Although this approach facilitated the
printing of Functionally Graded Materials (FGMs), a drawback surfaced: the
temperature of the starch-containing ink remained uncontrolled and led to defects
such as clogging.

Figure 5:Schematic representation of FGM printed

Given the relatively low total number of samples printed in this thesis, a strategy was
devised to enhance the data yield from each individual sample. Consequently, the
decision was made to fabricate FGMs featuring alternating sections of a porous
section and a pure zirconia section. This choice aimed to increase the number of
interfaces between the two layers for observation and analysis. The printing
parameters for the Functionally Graded Materials (FGMs) are detailed in Table 17.
Notably, the layer height was set at 0.23mm, resulting in each section being
composed of two distinct layers oriented at a 90° angle to each other.

Table 17:Printing parameters used for printing FGMs

Nozzle Nozzle Layer

Strand Temperature
Ink composition velocity diameter height
width (mm) (°C)
(mm/s) (mm) (mm)

10 vol.% starch, 30 Not

10 0.23 0.25 0.23
vol.% CEZ-12 available

40 vol.% CEZ -12 10 0.23 0.25 0.23 14

 Internal

3.2.2 Post processing:

i) Drying:

This step aimed to eliminate water content from the freshly printed green samples.
Upon completion of the printing process, each sample was promptly transferred into
a sealed container with 95% humidity to maintain its moisture level as seen in Figure
6a. Subsequently, the entire batch was transferred to a specialized humidity chamber
(HCP, Memmert, Germany) shown in Figure 6b. Within this controlled environment,
the temperature was set to 60°C, while the humidity steadily decreased from an initial
98% relative humidity (RH) to a final 30% RH over a span of 72 hours.

(a) (b)

Figure 6:(a) Picture of samples placed in a closed container immediately after printing
and (b)humidity chamber (HCP, Memmert, Germany)

ii) Debinding and sintering:

Densification of the printed green samples was achieved through a two-step process
involving debinding and sintering. The decision to adopt a two-step approach
stemmed from the incapability of the debinfing furnace to reach the required
temperature of 1450°C. The parts were debinded at 600⁰C for 1 hour in a muffle
furnace (Figure 7a) and pre-sintered at 1000⁰C in the same furnace for 1 hour with
heating ramp of 1⁰C/min and cooling ramp of 2⁰C/min. Sintering was carried out at
1450⁰C for 2 hours with a heating rate of 5⁰C/min in a Nabertherm furnace ( Figure
7b) in air.

(a) (b)
Figure 7:Muffle furnace (a) and Nabetherm furnace (b)
 Internal

3.3 Characterization of printed samples:

3.3.1 Shrinkage observations:

To find the optimal printing parameters the dimensions of the sintered samples were
measured using a vernier calliper. The overall shrinkage due to debinding and
sintering was measured.

3.3.2 Porosity measurement:

Since the samples are porous with a high percentage of open porosity, density
calculation using the Archimedes principle is not possible. Liquid intrusion
porosimetry following ISO 10545-3 standards was done to ascertain the %porosity
and percentage of open pores. This technique distinguishes open and closed
porosity and determines the bulk density of the sample using water as the
penetrating liquid.

The sample is initially weighed in air (mdry) using a precision scale (Sartorius BP 221
S) and then positioned within a beaker placed at the center of a desiccator. The
desiccator, linked to a vacuum pump, attains a negative pressure of 0.85 bar by
removing air. Subsequently, the beaker is filled with distilled water until the sample is
fully submerged, and the pump is activated. After a 2-minute interval, the desiccator
is vented, and the sample is weighed within the liquid (m wet,in) on the precision scale.
The sample is then extracted from the beaker, and its surfaces are dried with a cloth.
The dried sample is weighed outside the liquid (mwet,out).The liquid intrusion
porosimetry setup is depicted in Figure 8.

Figure 8:The liquid intrusion porosimetry set-up at MTM-KU Leuven

Table 18:Equations for calculations of apparent density, %open porosity

mdry ρtheoretical ∙ V material

mwet , out mdry + ρliquid ∙ V open pores

mwet ,∈¿ ¿ mdry −ρliquid ( V material +V closed pores )

 Internal

V open pores mwet ,out −mdry

ρliquid

%open porosity V open pores

%
V open pores +V closed pores

V closed pores mwet ,∈ ¿

mdry − −V material ¿
ρliquid

V apparent V material +V closed pores +V open pores

ρapparent mdry
V apparent

Where, mdry = mass of the sample prior to immersion in the penetrating liquid (g),
ρtheoretical = theoretical density of the studied material (g/cm 3), Vmaterial = volume of the
sintered sample (cm3), mwet,out = mass of the sample outside the penetrating liquid (g),
Vopen pores = volume of open porosity (cm3), mwet,in = mass of the sample inside the
penetrating liquid (g), Vclosed pores = volume of closed porosity (cm3) and ρliquid =
theoretical density of the penetrating liquid (g/cm3).

3.3.3 SEM characterization:

For further investigation, the structures of sintered green parts were observed by
scanning electron microscopy (SEM, XL-30FEG, FEI, The Netherlands). The
samples were mounted in epoxy resin, polished using the Struers automatic polishing
machine and coated with 5nm gold coating to improve electrical conductivity prior to
SEM imaging.

3.3.4 Micro CT characterization:

The micro computed tomography was done on sintered samples using the TeScan
Unitom XL with a 1mm Cu filter, X-ray source of 226 kV/15W and HW1, SW1, LOW
detectors. Tomography analysis was done using the CTan software (Bruker).
Projection images were reconstructed using the CTVox software. Dataviewer
software was employed to orient the cross-sectional images parallel to the trans axial
plane.
 Internal

References:
1. Daiichi Kigenso Kagaku co. Ltd., Certificate of analysis, 13-May-2022.

2. “Zirconia for Advanced Ceramics | Products | DAIICHI KIGENSO KAGAKU

KOGYO CO.,LTD.”DAIICHI KIGENSO KAGAKU KOGYO CO., LTD.,
www.dkkk.co.jp/english/products/pro03-1.html.

3.Sigma Aldrich, S4180-100G ,Certificate of analysis, 18-April-2023

4. Sigma Aldrich, P2443-1KG,Certificate of analysis, 17-November-2022

5. Zschimmer & Shwarz, Dolapix CE, Certificate of analysis, 09-March-2020