Universidade de Aveiro

Departamento de Engenharia de Materiais e Cerâmica (DEMaC)

Fabrication of silicon nitride-based parts by additive

manufacturing

Project thesis

Student: Mónica dos Santos Faria, 65096

Supervisors: Prof. Dra Susana Olhero; Dr. Filipe Oliveira
Date: february, 2023
 Abstract

Silicon nitride (Si3N4) based ceramics are well-established materials for several structural applications
due to their combination of properties, such as mechanical strength, resistance to thermal shock, high
hardness, and good wear resistance. Furthermore, manufacturing Si3N4 ceramic parts with complex shapes
by conventional subtractive techniques, in the industry, still is a great challenge that involves wear-
resistant machinery and very high costs.
Additive manufacturing (AM) technologies could be a promising solution to fabricate Si3N4 components,
due to their ability to form complex forms and high details. However, several difficulties have been
reported in the development of Si3N4 components with high densities and proper mechanical performance,
as a consequence of feedstock’ properties. Direct ink writing (or robocasting) is an AM technique with
high potential for ceramics, since it uses lower amounts of additives in feedstock when compared to other
suspension-based technologies, as for example vat photopolymerization. However, the optimization of
the ceramic paste is crucial to attain final dense parts.

Figure 1- Illustration of the schematic workflow.

Keywords: additive manufacturing, silicon nitride, robocasting, inks, mechanical properties,

microstructure.

II
INDEX
List of Figures ...................................................................................................................................... IV
List of Tables.......................................................................................................................................... V
List of Abbreviations ........................................................................................................................... VI
1. Motivation ....................................................................................................................................1
2. State of the Art .............................................................................................................................2
2.1 Silicon nitride .............................................................................................................................. 2

2.2 Conventional Processing methods of Silicon Nitride............................................................... 4

2.3 Additive Manufacturing of Ceramics: general principles ...................................................... 7

2.3.1 Inkjet Printing........................................................................................................................ 8

2.3.2 Stereolithography/Digital Light Processing .......................................................................... 9

2.3.3 Selective Laser Sintering..................................................................................................... 10

2.3.4 Laminated Object Manufacturing ....................................................................................... 10

2.3.5 Fused Deposition Modelling ............................................................................................... 10

2.3.6 Direct ink Writing ............................................................................................................... 11

2.4 Recent literature developments in additive manufacturing of silicon nitride ceramics ....... 12

3. Thesis objectives ........................................................................................................................16

4. Work Schedule ...........................................................................................................................17
4.1 Task Description ....................................................................................................................... 19

5. Preliminary work.......................................................................................................................21
5.1 Experimental procedure .......................................................................................................... 21

5.1.1 Printing silicon nitride-based samples by direct ink writing and sintering ......................... 22

5.1.2 Characterization of printed Si3N4-based samples ................................................................ 23

5.2 Results and discussion .............................................................................................................. 23

5.2.1 Raw materials and feedstock characterization for direct ink writing (DIW) ...................... 23

5.2.2 Sintered Si3N4-based printed parts characterization. ........................................................... 26

References .............................................................................................................................................30

III
List of Figures

Figure 1- Illustration of the schematic workflow. .......................................................................... II

Figure 2- Illustration of silicon nitride applications in the industry. ...............................................3
Figure 3- Crack propagation for (a) conventional ceramics and (b) in-situ toughened silicon nitride
ceramics. Adapted from reference [29]. ..........................................................................................4
Figure 4- Common process flow fabrication of Silicon nitride parts in the industry. Adapted from
[47]...................................................................................................................................................5
Figure 5- Illustration of the different methods for Silicon Nitride sintering ...................................6
Figure 6- Illustration of the most common AM techniques studied in the fabrication of silicon
nitride ceramics. Adapted from [60, 61]. .........................................................................................8
Figure 7- Illustration of the required steps to create a suitable ceramic-based ink for robocasting.
.......................................................................................................................................................12
Figure 8- (a) CAD model of cylindrical samples and infill patterning used; (b) robocasting printing
process of A-matrix based paste. ...................................................................................................23
Figure 9- Viscosity versus shear rate of A-matrix suspensions with 40 vol.% solids in presence of
(a) 0.2, 0.3 and 0.4 wt.% Dolapix PC 33 (D-PC33) and (b) 0.1, 0.2, 0.3 and 0.4 wt.% Dolapix A88
(D-A88). ........................................................................................................................................24
Figure 10- a) Flow curves of the A-matrix suspensions containing 40, 42 and 44 vol.% of solids
in the presence of 0.2 wt.% Dolapix A88, without and with carboxymethyl cellulose (CMC), (b)
example of a suspension with 44 vol.% with a shear thickening behavior and (c) same suspension
after CMC addition with shear thinning behavior. ........................................................................25
Figure 11- Storage modulus (G’) and loss modulus (G’’) versus shear stress for A-matrix pastes
containing different amounts of solids (36, 38 and 39 vol.%). .....................................................26
Figure 12- Surface fracture of samples with 39 vol.%, resulting from the flexural strength test.
Samples a) and b) were sintered as printed (without CIP) while sample c) was CIPed after printing.
Probable fracture origins are stressed with red circles, where: a) drying cracks and b) printing
pattern. ...........................................................................................................................................28
Figure 13- SEM morphology of non-CIPed and CIPed sintered Si3N4 printed parts after plasma
etching obtained with pastes pastes containing different amounts of solids (36, 38 and 39 vol.%).
.......................................................................................................................................................29

IV
List of Tables

Table 1- Properties of silicon nitride made from conventional processes. Adapted from [52]. ......7
Table 2- Characteristics of Si3N4 dense ceramics using different AM processes. ........................13
Table 3- Description of the tasks for the development of the PhD. ..............................................18
Table 4- Solids loading of A-Matrix initial suspensions, amounts of binders added and total solids
concentration in the final inks. ......................................................................................................22
Table 5- Properties of sintered A-Matrix samples obtained from pastes with 36, 38 and 39 vol.%
of solids, without and with cold isostatic pressure (CIP) after printing. .......................................26

V
List of Abbreviations

α-Si3N4: alfa- silicon nitride

β-Si3N4: beta- silicon nitride
AM: Additive manufacturing
BJ: Binder jetting
CAD: Computer-aided design
CIP: Cold isostatic pressing
DIW: Direct ink writing
DLP: Digital light processing
FDC: Fused deposition of ceramics
FDM: Fused Deposition modeling
HP: Hot pressing
HIP: Hot isostatic pressing
IJP: Inkjet printing
H-AM: Hybrid additive manufacturing
LENS: Laser engineered net shaping
LOM: Laminated object modeling
RBSN: Reaction bonded silicon nitride
SFF: Solid freeform fabrication
SLA: Stereolithography
SLS: Selective laser sintering
SLM: Selective laser melting
SSN: Sintered silicon nitride
WIP: Warm isostatic pressing

VI
 1. Motivation

Silicon nitride is a well-established ceramic material for several structural applications at room
and high temperatures, thanks to a combination of high mechanical strength, hardness, wear
resistance and thermal shock resistance [1]. Cutting tools, protection against high speed impacts
and biomedical devices are examples of application fields for this material [2]. These ceramics
are commonly produced at industrial level by powder processing. Distinct sintering processes
can be used to attain high densification levels, a mandatory feature to achieve the expected high
performance [3–5].
To obtain complex geometries of Si3N4 ceramics by conventional processing, machining post-
processes are commonly used. These are time-consuming, costly and unsustainable, producing
large amounts of wastes resulting from the cutting and grinding operations [4, 5]. Complex
geometries with fine details are difficult to obtain or even impossible to produce with traditional
processing methods and can be developed with additive manufacturing (AM) [6–10]. In what
concerns Si3N4 ceramics, reaching high densities and adequate mechanical performance are the
main drawbacks for industrial implementation of AM, mainly due to the complications in
developing the proper feedstock for each AM technology [11].
Binder jetting (BJ), selective laser sintering (SLS), selective laser melting (SLM),
Stereolithography (SLA), Digital Light Processing (DLP), Direct Ink Writing
(DIW/robocasting) and Direct Photo Shaping (an AM technique which combines robocasting
with photocuring), have been the technologies mentioned to date in literature for the AM of
Si3N4 ceramics [6, 9, 11]. Powder-based AM technologies, as BJ and SLS, commonly uses
granulated powders as feedstock to achieve a proper printing flow. The main concerns are
related to the high porosity in the final parts [11, 12]. Regarding technologies that use
suspensions as feedstock, such as photopolymerization (SLA and /or DLP) and extrusion based
categories (DIW/robocasting), maximization of the amount of ceramic powders in the pastes or
suspensions, their homogeneity and stability over time, the rheological characteristics, the
burnout of binders and large shrinkages of the final parts are still the challenges to overcome
[11, 13–16]. Therefore, the present PhD proposal intends to explore the DIW technique in the
fabrication of complex prototype silicon nitride structures [15, 17, 18] for hard tool
applications. In addition, to allow the use of highly concentrated suspensions with small
amounts of additives [19], this technology should promote the reduction of waste in the
fabrication of this type of hard material, which are interesting advantages from an industrial
point of view. The proposal will be evaluated in a straight collaboration with Palbit S.A, a
company that develops hard metal and ultra-hard materials tooling solutions for several
applications such as: automotive, mold and die, power generation, shipbuilding, wind energy
and general engineering.

1
 2. State of the Art

2.1 Silicon nitride

Silicon nitride (Si3N4) is a ceramic material that has been found on earth as a natural constituent
of presolar meteoritic grains, known for its excellent mechanical and thermal properties and is
used for numerous applications [20]. In the beginning of the 20th century, silicon nitride was a
small academic curiosity. Then, due to its potential as a ceramic, the interest in this material
increased, namely in the last 60 years [21]. In a patent registered in 1907, Si3N4/SiC composite
ceramics were developed, by pressing and heating a combination of 30Si/70 SiC in pure N2, to
turn the Si content into Si3N4 [22]. The early 1960s saw a notable acceleration in the
development of Si3N4 ceramics as prospective high temperature engine materials. This was the
result of an intentional and methodical search for new materials with the right qualities namely,
with resistance to thermal shock [23]. Later on it was discovered that by adding specific
sintering aids to silicon nitride and using hot-pressing in the sintering process it was possible to
attain a much stronger material [24].
Si3N4 has been employed in industrial applications, and its mechanical properties have been
enhanced by improving the processing techniques and using additives to produce composite
structures. Silicon nitride is nowadays used for several applications in aerospace, military, and
biomedical fields (Figure 2). The use of silicon nitride as a cutting tool has represented an
attractive market for this material, mainly due to its high wear resistance. Moreover, it has been
used as a structural material in the production of engine, turbine and bearing parts, protective
coatings and heat exchangers and even for ballistic applications [1, 25, 26].
Features such as low density, which results in reduced inertia, and high resistance to wear, made
possible the use of silicon nitride in conventional internal combustion engines and adiabatic
diesel engines. In the case of the combustion engines, exhaust valves, valve seats and bearings
are the main commercialized silicon nitride components. It is widely used in high performance
aircrafts and even in the National Aeronautics and Space Administration (NASA). In 2010,
silicon nitride demonstrated to be interesting for instrumental applications, being used, for the
first time, in cryomachinery at the Space Shuttle main engine [27]. The dielectric properties of
silicon nitride also make it a desirable material for use in the manufacture of radomes (protective
coverings that shelter the antenna assemblies of a radar set), especially for aircrafts. Recently,
it has also been explored for biomedical applications, such as bone tissue engineering, due to
its biocompatibility. There are studies that showed the osseous fixation and bone fusion in
spinal surgery by using silicon-nitride based materials [28, 29].

2
 Figure 2- Illustration of silicon nitride applications in the industry.

Silicon nitride ceramics are commonly produced industrially by powder processing. Also,
distinct sintering processes can be used to attain high densification levels, a mandatory feature
to achieve the expected high performance [3–5]. The full densification of these ceramics by
solid-phase sintering is difficult to achieve, due to the covalent character of the chemical
bonding (Si-N) involved in this compound [30]. In this way, it is necessary to promote sintering
with the formation of a liquid phase, by using various sintering additives. During high
temperature processing, these sintering additives react with the silicon oxide that spontaneously
coats the Si3N4 powders, creating a liquid phase at lower temperatures, to increase mass
transport and then the decomposition temperature of silicon nitride, consequently reducing the
porosity of the material [31, 32]. This liquid can wet the silicon nitride particles, facilitating
their decomposition, diffusion and reprecipitation. When cooling, this fluid solidifies and
becomes an amorphous phase or a partially crystallized glassy phase around the β-silicon nitride
grains [33, 34]. Some of the most common sintering additives are MgO, Y2O3 and the
combination of Y2O3 with Al2O3 [35–38], making possible the obtention of intergranular phases
with lower melting temperatures than the decomposition of Si3N4. Yttria is an excellent additive
that leads to growth of elongated β- Si3N4 grains and helps to increase the mechanical
properties.
Si3N4 is often toughened in situ, due to its elongated rod-like grains, that make it more difficult
for a crack to spread through the grains (Figure 3). The irreversible recrystallization of α- Si3N4
into β- Si3N4, during sintering, enables this in-situ toughening and allows the microstructural
control of these ceramics [39].

3
Figure 3- Crack propagation for (a) conventional ceramics and (b) in-situ toughened silicon nitride
ceramics. Adapted from reference [29].

These materials have long been manufactured using pressure-assisted sintering techniques
including hot pressing and spark plasma sintering. Although these methods can create high
density components with better material characteristics, their widespread applicability is
restricted to simple shapes [40]. Due to the excellent intrinsic mechanical properties of this
material, manufacturing parts of complex shapes by conventional subtractive techniques
(material machining) is a challenge that involves time consuming operations and very high final
costs [5]. In order to overcome these disadvantages, near-net-shape manufacturing techniques
have been explored, making suitable the fabrication of pieces with a shape approximate of the
final one, where the machining and finishing processes are reduced or even non-existent [11].
Several techniques can be highlighted for those accomplishments including injection molding,
gel casting, and more recently, additive manufacturing. Obtaining reproducible suspensions
with consistency and stable flow characteristics is another challenge for these manufacturing
processes [5].

2.2 Conventional Processing methods of Silicon Nitride

Advanced ceramics, as Si3N4, can be produced by different processing routes, as shown in
Figure 4, as powder processing that compacts dry powders in a simple geometry or by colloidal-
based technologies involving the casting of slurries in a mold (Figure 4) [41]. The most
common powder processing methods are uniaxial pressing, isostatic pressing, injection
molding, while slip casting and tape casting are colloidal based ones. Benefits related to the
high homogeneity of all components can be stated for colloidal base technologies when
compared to dry pressing ones. Though, in wet shaping technologies, final densities are strongly
dependent on the particle packing behavior and solids load in suspensions. As for example,
Albano et al. [42] developed a concentrated Si3N4 slurry with sintering additives (Y2O3 and
Al2O3) and concluded that a higher density of slip cast green compacts can produce higher
sintered densified specimens. On the other hand, hydroxide precipitates were studied by Shaw
et al. [43] to create sintering additives with fine particles aiming to attain Si3N4-based
homogeneous green compacts.
However, dry forming processes are, currently, far more commonly used in industry than wet
forming techniques since they are the cheapest approaches. Indeed, the liquid removal in wet
forming is very energy- and time-intensive, while similar drawbacks occur in the polymer
removal from plastic forming routes such as injection molding. Therefore, wet forming
techniques are being used only when dry forming does not provide the performance required
4
[23, 25, 44]. For both kinds of processes, the mixture of raw-materials and their particle size
distribution are important parameters to control. Usually, ceramic powders are commonly
mixed with an organic binder and other additives (as deflocculants and plasticizers). The
mixture can be homogenized and milled for several hours to improve the particle size
distribution. After that, the powders should present adequate particle size to be thermally
treated, according to the intended application.
Following the forming process, the organic binder is removed through a controlled heating
process, then sintering in a furnace at a high temperature in different atmospheres, with or
without associated pressure, that gives the component its final material properties and
microstructure [45]. To guarantee that items have the proper surface finish and adhere to the
requisite tolerances, further post-processing operations like machining, grinding, and polishing
are frequently essential [46].

Figure 4- Common process flow fabrication of Silicon nitride parts in the industry. Adapted from
[47].

Concerning the sintering process of silicon nitride after the conformation process, there are
different methods to attain the densification, as shown in Figure 5.

5
 Figure 5- Illustration of the different methods for Silicon Nitride sintering

Different methods have been explored: with associated pressure as hot pressing (HP) and hot
isostatic pressing (HIP); pressureless sintering and reaction bonded silicon nitride (RBSN) [48].
For the sintering process, either atmospheric pressure or a higher nitrogen partial pressure may
be used, depending on the concentration of additives needed for the liquid phase. The
techniques that combine temperature with pressure (HP and HIP) result in silicon nitride parts
with better mechanical behavior. However, HP processes present limitations in terms of
manufacturable geometries , and the costs associated with this technology are usually high. In
HIP , the compacted silicon nitride powders are heated in a N2 atmosphere at temperatures
above 1700 ⁰C, and final densification is reached under 50 MPa (HP) to 200 MPa (HIP)
pressures [49], being another advantage the reduction of the amount of additives. RBSN
consists in the production of a ceramic material from the heating of a silicon powder compact
in an atmosphere of nitrogen gas. The nitridation reaction occurs at 1200 ⁰C and temperatures
can reach a maximum of 1450 ⁰[21, 25, 34, 49, 50]. The major advantage of this process is the
inexistence of large dimensional changes. However, the porosity with this method, seems to be
much higher and consequently, its mechanical properties lower than the ones attained with the
alternative processes. Pressureless sintering, normally requires sintering additives and a
temperature range from 1700 to 1850 °C [30, 50, 51]. This sintering method often provides
good mechanical behavior, such as high strength, due to its high density (less than 1% porosity
and about 750 MPa bending strength).

Table 1 presents examples of the most common silicon nitride properties obtained from
conventional processing methods and sintered at different conditions.

6
Table 1- Properties of silicon nitride made from conventional processes. Adapted from [52].

Relative Flexural Fracture

Conventional processing Hardness Refer
Density Strength Toughness
techniques (GPa) ence
(%) (MPa) (MPa m ½)
Axial pressed
[53]
+ 600MPa CIP, HIP 99.3 950 6 16.3
[5]

Uniaxial pressing +
pressureless sintering 99 ~750 6 14-15 [54]

Gas pressure sintering 2000

ºC 99.9 920 3.9 18.4 [55]

Coating powder + slip casting 98-99 [30]

910 7 15
+ pressureless sintering [42]
475- [56]
94-99 - 14
Tape casting 1000 [57]

Observing the table, it is possible to verify that that the use of pressure provides great
improvements in the mechanical properties of the material.

2.3 Additive Manufacturing of Ceramics: general principles

The additive manufacturing (AM) of ceramic components presents a set of promising

technologies, with unique manufacturing capabilities in terms of complexity, although it is still
taking its first steps in the industry.
The interest of the industrial and academic communities has grown more and more, as a result
of the challenges that these disruptive technologies may present, as well as the countless
innovative opportunities that AM present at several levels as product design, material selection,
market response and circular economy [6, 58, 59]. Since its appearance, several polymers,
metals, ceramics and composite’ parts, have all been created using AM. In comparison to
polymers and metals, ceramics and ceramic matrix composites are still in the early stages of 3D
printing manufacture [8]. Among the numerous limitations, it can be mentioned: low resolution,
weak surface finish, limited part geometries possible to obtain, low densities and poor
mechanical properties after sintering [6, 8]. The inherent properties of ceramic materials and
their processing conditions may be the source of the difficulties in the AM processes
development for these materials.
AM includes different processes and technologies, however the sequence of steps is common
to all processes, i.e:
(1) creation of the three-dimensional digital model of the object;
(2) file conversion to allow the AM process to deposit the material layer by layer;
(3) printing;
(3) post-forming processes.
7
The different AM technologies are distinguished by the way in which the layers are build and
adhered, through energy or print-heads, in different based-materials: powder, filament or
suspension.

Figure 6 presents the AM technologies mentioned to date in literature for Si3N4 ceramics [6, 9,
11], including fused deposition modeling (FDM), stereolithography (SLA), selective laser
sintering (SLS), laminated object manufacturing (LOM), binder jetting (BJ), and direct ink
writing (DIW)/ robocasting. The principle behind each technology, in particular for ceramic
materials, is briefly described below.

IJP

Figure 6- Illustration of the most common AM techniques studied in the fabrication of silicon nitride
ceramics. Adapted from [60, 61].

2.3.1 Inkjet Printing

The term "inkjet printing” (IJP) is also known as material jetting. This technique is based on
the 2D printer technique of applying small ink drops on substrate using a jet. A well-dispersed
ceramic ink is deposited selectively, to directly shape ceramic pieces onto a build substrate.
Because of its low surface roughness and great dimensional accuracy, IJP is also regarded as a
potent microfabrication technique [58]. Furthermore, it also enables the fabrication of
functionally graded composites by precisely controlling the deposition of components at the
voxel scale. The exploration of IJP of ceramic matrix composites has been limited since it is
difficult to maintain printing consistency and dependability due to substantial nozzle blockage
[62].
Concerning the fabrication of dense silicon nitride parts, few reports appeared in literature.

8
 2.3.2 Stereolithography/Digital Light Processing
Stereolithography (SLA) is a vat photopolymerization technology based on the curing of a
photosensitive resin containing ceramic particles (aiming to obtain ceramics). During the
process, the slurry is cured selectively, with high precision, by a light source from a laser. The
tank contains the platform and the liquid resin, that after cured became the solidified printed
part. After the first layer, in order to allow fresh slurry to flow or be wiped over the top of the
cured section, the base of the vat is then lowered by a brief distance. The procedure is then
carried out until complete the item [6, 10, 63, 64]. This method was firstly created for the
additive manufacture of photomonomers-based polymer components, but it may also be used
to produce green bodies by filling the photomonomers with a significant volume proportion of
ceramic powder (ideally higher than 40 vol%). After the polymer has been burned out, post
processing occurs similarly to conventional ceramic green bodies.
SLA is capable of producing precise and high-resolution ceramic parts. Despite being difficult
to suspend accurately deagglomerated Si3N4 particles into resins (as a single AM step
procedure), there are combinations of various AM techniques in the literature to create Si 3N4
part, as creating multi-ceramic composite with >45 vol.% solid content. As many AM
techniques, the maximum solid loading attained, with suitable properties, usually creates more
dense final parts [65]. For that, the slurries must have low-viscosity with a shear thinning
behavior and high curing depth, which leads to use surface modifier- as silane coupling agent-
directly as the dispersant [66, 67].
As with many methods, there are limitations on the largest component that can be printed due
to cracking brought on by part shrinkage and difficulties with large piece debinding. The time
needed to perform debinding without delamination or cracking becomes, sometimes
prohibitively long for parts with huge monolithic sections. Even for small pieces, debinding
could take several days [68]. One of the proposed solutions to address this problem is the heat
treatment of these powders as a pre-oxidation method [69] from 400- 1200 °C to create a layer
of SiO2 thin film on the surface, which also reduced the sintering temperature.
Digital light processing (DLP) uses a projector to selectively expose an entire cross-sectional
slice from a computer- aided design (CAD) on the photosensitive liquid resin surface at each
defined time, which shows faster build speeds than SLA [70]. Normally, the UV light is below
the tank. As in SLA, due to the high amounts of resin-based material removed during the
burnout step, the mechanical properties of the final ceramic printed parts are fairly low after the
debinding.
Despite this technique has being largely used for Al2O3 ceramics, it represents a challenge for
Si3N4, mainly due to the strong UV absorption of Si3N4 ceramics that inhibits the
polymerization of the resin. So, due to the significant refractive index of these slurries, the
curing ability is reduced [71]. When the UV wavelength is 405 nm, for instance, Si3N4 has a
refractive index of 2.0978, which is higher than common oxide powders like SiO2 (1.5571) and
Al2O3 (1.7555), whereas the refractive index of the majority of photosensitive resins is about
1.5 [72]. It suggests that there is a greater difference in refractive index between resins and
Si3N4 ceramic powder.

9
 2.3.3 Selective Laser Sintering
Powder-based AM technologies, as SLS, commonly uses granulated powders as feedstock to
achieve a proper printing flow. The main concerns are related to the high porosity in the final
ceramic parts [11, 12]. The method uses the thermal energy of a high-power laser to agglutinate
particular portions of a powder bed material. A slice of the part's shape is determined by the
laser created pattern. After finishing the layer, the component is lowered, and a new coating of
powder is rolled over it. This technique has the benefit of being able to work with a wide range
of materials, including metals, ceramics, polymers and other powders [45, 73].
As it is a powder bed process, there are virtually no limitations on the type of features that can
be printed. However, in reality, the benefits are far outweighed by some serious challenges
which have not yet been overcome. As with all powder bed techniques, closed hollow cavities
are not possible (as the powder cannot be removed from these), and delicate structures are
difficult as they can easily be damaged in the powder bed removing step. Nevertheless, the
greatest issue is the residual stresses- from rapid heating succeeded by solidification. This
disadvantage may cause cracking or even complete structural collapse [63, 74, 75].

2.3.4 Laminated Object Manufacturing

Laminated Object Manufacturing (LOM) is an AM technique that allows the solid freeform
fabrication (SFF) where a part is built sequentially from layers of sheets, being initially created
with polymer or paper sheets. The method is based on the idea of fabricating the object by
progressively laminating its component cross-sections [76] where a laser is used to cut a sheet
of material into the shape of a 2D slice of the target item. The next slice is created by lowering
this shape by one layer height, applying a new sheet of material using a heated roller, and cutting
it with the laser once more.
Except for closed cavities, there are no restrictions on the features that can be printed, and the
technique is well suited to layers of materials like paper. However, ceramics have only
occasionally seen its application. The majority of the work presents this technique as an initial
experiment that produce low green densities, calling for additional pressing/infiltration
procedures [77].
The SFF of advanced complex-shape Si3N4 structural components from LOM green forms has
been demonstrated as a viable process [11, 64, 76]. The process included the Si3N4 sheets
preparation by aqueous tape casting, then their lamination, and final sintering combining hot
pressing (HP) and spark plasma sintering [78].

2.3.5 Fused Deposition Modelling

FDM is an AM technique inserted into the material extrusion category. Material extrusion
involves the selective deposition of material using extrusion from a nozzle. The benefits of
material extrusion include low cost, a wide range of material systems that are applicable, and
easy and convenient operation. Material extrusion can be categorized into two types: standard
temperature extrusion and high temperature extrusion [79].
While normal temperature extrusion usually uses direct ink writing or robocasting, high
temperature extrusion primarily uses fused Deposition modeling (FDM). FDM is a high
temperature extrusion forming process that involves heating polymer-based filament and

10
extruding through a nozzle followed by the solidification onto a Z-stage platform with the
desired geometry. Each slice of a CAD model has a filament of molten polymer deposited in a
specified pattern [45, 80]. Using a hot die and electric motors, the molten polymer is extruded
from a long, flexible, solid filament. In addition, to occasionally using an integrated fan, the
newly extruded material is continuously cooled by conduction from the substrate. Usually,
solidification occurs very shortly after the deposition, keeping the desired part’s shape.
Fused deposition of ceramics (FDC) is a technique based in FDM which uses a filament
containing a moderate concentration of ceramic particles [81]. In FDC, the thermoplastic
polymer acts as a carrier and binder for the ceramic particles as Si3N4, as the material passes
through the liquefier extruder head and the nozzle. The liquefier tool path vector moves in the
X and Y directions, controlled by the computer. After that, the printed green part, suffers a
bonder removal and sintering process to achieve a fully dense material [82]. FDM has
increasingly been used in commercially available devices due to its straightforward working
concept and affordable startup and operational costs.
Although this technique may create certain defects, some post-print methods could reduce it-
as, for example warm isostatic pressing (WIP). Raising the WIP’s temperature to 70 and 90 ºC
[83] it is possible to build objects with undetected defects in the X-ray radiographs. There are
several parameters to obtain a proper filament with ceramic particles and an efficient printing:
i) low viscosity with high solids loading (~50 vol.%), without large particles that may clog the
nozzle and sufficient stiffness and column strength;
ii) optimization of flow parameters and deposition to create dense green parts;
iii) a binder with the capacity to bond adjacent roads and layers during the deposition
iv) heat treatment and sintering parameters to avoid warping or cracking and fully densification.

2.3.6 Direct ink Writing

Robocasting, also known as direct ink writing (DIW), was developed by Cesarano et al [84].
DIW is a material extrusion technique that uses a high loaded suspension named as ink or paste.
A 3D object can be created in sequential layers by a CAD drawing/ depositing a ceramic paste
through an orifice. Usually, a high concentrated ink is placed inside a container that presses
the paste through a small orifice nozzle, depositing the filament on a substrate, according to the
previously established drawing. When the first layer is created, the nozzle moves in Z to deposit
a next layer until the object is completely finished.
The main step in this process is to achieve an ink suitable for extrusion, with specific rheological
characteristics. In fact, the mechanical integrity of the components obtained by this technology
relies on the rheological properties of the feedstock [85]. It is also crucial to have a high and
predictable volume percent of solid ceramic powder in the suspension for successful deposition
by DIW. The solids loading affects the final bead size, as well as the slurry’s viscosity and
rheology.
In comparison with photopolymerization, DIW uses lower amounts of organic additives, which
is an advantage as it avoids cracks and large shrinkages during the burnout and the sintering
steps of bulk ceramic parts [66, 68, 86].
The fabrication of Si3N4-based ceramics by DIW, has been already explored in literature but it
is yet scarce and highly focused on lattice structures or porous devices, as scaffolds for
biomedical applications [16, 85, 87]. There is unanimity in the literature on the need for highly
refined starting powders with a suitable particle size distribution to maximize compatibility and
11
sinterability of the printed parts [88–90]. Furthermore, some authors mention that solid loads
with bimodal distributions induce a reduction of the feedstock viscosity when compared to
suspensions manufactured with monomodal distribution [12, 91], for the same solids loading.
Shear thinning behavior and high elastic modulus are needed to guarantee simultaneously, a
proper flow though fine printing nozzles and filament shape retention just after printing, to
assure weight support of the subsequent layers. These characteristics are presented in Figure 7.

Figure 7- Illustration of the required steps to create a suitable ceramic-based ink for robocasting.

2.4 Recent literature developments in additive manufacturing of silicon nitride ceramics

Table 2 resumes the most relevant studies presented in literature till date, related to the
fabrication of dense silicon nitride parts by different AM processes.
There is not a vast number of studies about silicon nitride additive manufacturing. Despite the
mechanical properties and characteristics of the material yet differ from conventional mode,
some results may be considered with potential interest.

12
Table 2- Characteristics of Si3N4 dense ceramics using different AM processes.

Processing Relative density Mechanical properties

Ref. Description Sintering method
technology (%)
HIP 1800 ºC FS 725 MPa
99.0
low cost Si3N4 powders 35 MPa 0.5 h
(Shenhai Nitride Company)
LOM SPS 1600ºC FS 650 MPa
[78] 40 vol.% Si3N4 suspension 98.1
30 MPa 3 min
55.3 wt. % [Si3N4+ Al2O3+
[56] LOM Conventional 1800 ºC – 1 h 94.3 BS 475 MPa
Y2O3] suspensions
FS 400 MPa
green tapes Si3N4
[76] LOM 1750 1800ºC – 2 h N2 97 FT 5.5-7.5 MPa.m1/2
1457 HV
Lithography-
40vol.% SiAlON powder in a FS 764 MPa
[68] based ceramic Conventional 1800 ºC – 4 h 99.8
photocurable resin 1500 HV10
manufacturing
45 vol.% [Si3N4+ 5 wt% Y2O3 FT 5.82 MPa.m1/2
[92] SLA Conventional 1750 ºC – 2 h 95.0
+3 wt% Al2O3] + prepolymer 1463 HV10
Vacum debinding
44 vol.% Si3N4+ Al2O3+ Y2O3 FS 800 MPa*
[14] SLA 1800 ºC 3 h 98.28%
suspension
N2
-
Si3N4+ 5% Al2O3+ 3% Y2O3 BS 592 MPa
[93] SLS CIP 225 MPa (x2) 82
powders -
Si3N4–Si2N2O-BN composites 280 MPa CIP B.S 651 MPa,
[74] SLS -
radomes 1750 ºC- 3 h, N2 FT 6 MPa.m1/2
SLS +
Si3N4, SiC, Al2O3 powders for 1500 ºC
[94] infiltration 92 FS 76.48 MPa
Si3N4–SiC/SiO2 composites
process

13
 30-35 vol.% [Si3N4 coated with FS 149.2 MPa
[72] DLP Conventional 1800 ºC – 2 h 85.0
Y2O3+Al2O3] slurries -
transparent Si3N4-SiO2 (slurry
FS 77 ± 5 MPa
[95] with 50 % solid [Si3N4+10% -
DLP 1350 ℃
Al2O3])
Si3N4 powders in prepolymer 1700 ºC FT 6.57 MPa.m1/2
[96] DLP 80-95
and photoinitiator TPO 30−50 Mpa 1348 HV10
1800 ºC 3 h, N2
[82] F.S 824.74
55 vol. % GS-44 Si3N4 powder FDM pressure 2.5 MPa 98
[83] 345 HV20
WIP
32.5 vol.% Si3N4 powder +
FT 4.4 MPa.m1/2
[58] yttrium–aluminium–garnet IJP Conventional 1780ºC – 2 h 96.0
1700 HV0.2
powder
61 wt.% [Si3N4+Y2O3+Al2O3] 1700 ºC 2h N2
[16] DIW FS 552 MPa
biomedical applications 200 MPa HIP 1700 ºC 2h 99
43 vol.% [Si3N4+12 vol.%
[18] DIW 1700 º C- 3 h 97.3 -
(Y2O3+Al2O3) powder
40 vol.% [92 vol.% Si3N4+
3vol.% Y2O3+5 vol% Al2O3] FS 348 MPa
[19] DIW 1750 º C- 2 h 98.4
paste

*there is no information about the used method to evaluate the flexural strength of the printed parts
Where: FS: Flexural Strength; BS: Bending Strength; FT: Fracture Toughness; LOM: Laminate Object Manufacturing; SLA: Stereolithography; IJP: Inkjet
Printing; DLP: Digital Light Processing; SLS: Selective Laser Sintering; FDM: Fused Deposition Modelling; WIP: Warm isostatic processing DIW: Direct
Ink Writing; HIP: Hot Isostatic Processing and SPS: Spark Plasma Sintering.

14
As shown in the Table 2, the literature presents already some reports using AM technologies
that provide final parts with relative densities higher than 95 % and interesting mechanical
properties. However, most of those studies used specific sintering methods (HIP, WIP and
plasma sintering) and high sintering temperatures, as the results presented with LOM and
FDM techniques [56, 78]. Specifically in LOM, Shichao Liu et al.[56] made an initial slurry
containing 49.8 wt.% Si3N4, 3.44 wt.% Al2O3 and 2.06 wt.% Y2O3 for tape casting. Dry tapes
were created for subsequent stacking and production of the various silicon nitride components.
The green 3D parts were made by stacking the tape pieces layer by layer and then pressureless
sintered at 1800 ºC for 1h. Some samples presented uniform distribution of the ceramic
particles and small pores (0.13 µm) in the green tape, resulting in a densification around
~93.7%. It was mentioned the precipitation of the ceramic particles during tape processing
and also some roughness of the bottom surface. Even so, the warping of the components was
minimal and strength values achieved, reached 475 MPa.

Regarding SLS and IJP techniques, the relative densities reported are not very high (85 and
96 %, respectively, Table 2), leading to the need of post processing methods as cold isostatic
pressing (CIP). Kejie Wang et al. [74] developed high-strength and wave-transmitting Si3N4–
Si2N2O-BN radome composites. Despite the relative density was 34 %, the mechanical
performance of the parts met the requirements for radomes applications, when CIP was used
as post-processing, before the sintering step. After sintering, the bending strength and
dielectric constant of the Si3N4 ceramics were 651 MPa and 3.48, respectively. The authors
concluded that the post-processing method increased the properties drastically, from values
of 12 MPa of strength (without CIP) up to 225 MPa (after 1 CIP), reaching 592 MPa after 3
CIPs [93].

As mentioned before, due to the low Si3N4 absorption of laser beam energy,
photopolymerization techniques as SLA can be really challenging in the development of high
dense parts, demanding other post-process procedures [68]. In fact, Si3N4 samples processed
by light curing techniques (SLA/DLP) presents a better surface finishing when compared to
other AM techniques, as for example DIW/robocasting. However, a high variability of
flexural strength values have been reported (150-764 MPa) compromising the final
application of the bulk ceramic part [58, 68, 72]. Dispersing the ceramic (specifically Si3N4)
particles in the photocurable-based resin in high concentrations is one of the main difficulties
reported by SLA/DLP. Using low solids load, results in long debinding steps and high
shrinkages after sintering. Cracks and several defects resultant to the debinding process are
also common, mainly for bulk ceramic parts. According to some research’ findings [66], to
improve the photocuring performance, Si3N4 surface modification is required. Also, the
temperature of the environment has a significant impact on the viscosity of Si3N4 photocurable
slurries, being verified that the viscosity significantly dropped as the temperature increases
[70]. Hence, the oxidation with heat treatment process could efficiently improve the curing
thickness and stability of Si3N4 slurry. Meng Li et al. [69] fabricated samples by DLP using
Si3N4 powder coated with Al2O3-Y2O3 as sintering additives, starting from an initial well-
deagglomerated slurry with a solid loading of 30-35 vol.%, achieving 85.4% relative density.

15
Compared to SLA/DLP, direct ink writing (DIW) has been revealed as a promising technology
for ceramics, since it’s not so difficult to prepare a ceramic-based ink with high concentration
of solids and low quantities of additives. However, the literature works that used DIW and
pressureless sintering do not reach relative densities higher than 98.4 %, while relative
densities higher that 99 % are only attained when was used as post-processing and/or HIP
during sintering [16]. Zhao S. et al. [16] reported the ability to fabricate Si3N4 ceramics by
robocasting using a mixture of low and high molecular weight polyethylene imine (PEI) and
hydroxypropyl methylcellulose (HPMC) as binders in a paste containing around 62 wt.% of
solids (Si3N4 and Al2O3/Y2O3 as sintering aids). Almost fully dense Si3N4 samples with
flexural strength of 552 ± 68 MPa were obtained by using HIP after sintering.
Recently, Deiner et al. [18] stated the influence of using different printing patterns in residual
porosity of Si3N4 components produced by DIW. The authors concluded that the print infill
pattern (aligned, hexagonal, diagonal) affected the amount, size, and shape of pores in the
final components. The maximum relative density reported was 97 % for a feedstock paste
containing 43.8 vol.% of solids. Besides porosity, fast drying and bending of the parts during
drying step were underlined as needed matters to explore and control in this technology.
For these presented results, studying optimized silicon nitride-based pastes, with proper
adjustments, represents a field of interest as an opportunity to develop dense parts by DIW.

3. Thesis objectives
The main goal of the present PhD proposal is the development of silicon nitride complex parts
by an extrudable-based additive manufacturing technology, named robocasting. Highly dense
silicon nitride ceramics should be attained by studying the inks’ development, printing
parameters and sintering schedule. Silicon nitride parts with a full densification, suitable
dimensional resolution, and similar mechanical performance comparable with similar parts
made by conventional techniques should be produced.
To attain the main goal, the following objectives are envisioned:
- Development of stabilized and high concentrated silicon nitride suspensions with shear
thinning behavior.
- Development and characterization of inks with rheological behavior proper for
printing by robocasting.
- Evaluate the most appropriate printing parameters to attain fully dense ceramics.
- Evaluate and adequate the post-processing heat treatments and sintering step.
- Characterization of the printed parts
- Prototypes creation for industrial tests and application.

This thesis project results from a joint collaboration between the University of Aveiro (UA)
and the company Palbit. This collaboration started with 3D CompCer project POCI-01-0247-
FEDER-047060 where the main goal was the development of cutting tools with internal
refrigeration channels by AM. The experimental work will be done mainly in the Departament
of Materials and Ceramic Engineering (DEMaC). Some specific heat treatments and the
performance of the final prototypes will take place in the Palbit company.
16
 4. Work Schedule

Table 3 presents the different foreseen tasks for the development of the work during the PhD.

17
Table 3- Description of the tasks for the development of the PhD.

18
 4.1 Task Description
Task 1: State of the art and review of the literature
This task includes a review of the literature concerning silicon nitride ceramics, its fabrication
and properties usually attained by conventional processing and the state-of-the art concerning
the fabrication of this material by additive manufacturing. It is intended to identify the
advantages and disadvantages for the processing of silicon nitride by the different AM
technologies and clearly establish this doctorate program contribution to the materials science
and engineering area, namely concerning materials and the AM technology selected.
Structural and mechanical performance of this material in literature will be stated and
compared with the results that will be accomplished in the present PhD proposal.

Task 2: Development and characterization of silicon nitride suspensions and inks as

feedstock for robocasting
This task starts with the selection and preparation of raw materials, as powder mixture and
milling, and their characterization by particle size distribution, particle shape and crystalline
phases composition. Then, aqueous-based suspensions and inks should be developed and
properly tuned for printing by robocasting. Pastes for printing by robocasting must meet two
criteria: (i) pseudoplastic behavior and viscoelastic response, i.e., flow through a printing tip
with fine diameters (< 1 mm) and immediately retain the shape after printing in order to
withstand the weight of the back layers; (ii) present high solids concentrations to minimize
part shrinkage during drying and sintering. To achieve these criteria, it is necessary to optimize
several parameters as the nature and quantity of deflocculants and other rheological modifiers
as organic binders and thickening agents. The selection of these agents will be based on zeta
potential and rheological measurements, analyzing the viscosity and viscoelasticity of the
suspensions and pastes in viscometry and oscillatory modes using a rheometer.

Task 3: Printing and post-processing of silicon-nitride parts

The quality of the printed parts depends not only on the rheological properties of the ink, but
also on the printing parameters. So, in this task the printing parameters will be optimized
considering the rheological properties of the paste and the complexity (geometry, size) of the
piece. In a first step simple geometries (cylinders, parallelepipeds) will be designed to evaluate
the influence of printing speed, printing tip diameters (in the range of 150 m -1 mm) and in-
fill patterning on the surface and geometrical quality of the green printed part and
subsequently on the sintered one (Task 4). Optical analysis, scanning electronic microscopy
and micro computed tomography (-CT) will be used for parts characterization after printing
to assess possible defects.
Furthermore, the drying step is also critical in this technology. For that, the environment must
be controlled with humidity and temperature to prevent defects and cracks. After that, since it
is not expected to use high amounts of organic additives, the burning of binders will be
normally carried out at temperatures between around 500 ºC. Nevertheless, this procedure
19
may be analyzed, according to the added binders. Thermal analysis will be performed to
support the debinding step. Post-processing procedures as cold isostatic pressure (CIP) will
be tested to increase the final density of the parts, assuring the reproducibility of the process.
The sintering schedule of the samples will be studied, based on the knowledge already
acquired by the research group investigation for this particular ceramic material [30].

Task 4: Characterization of the silicon nitride sintered final parts

The characterization of the printed and sintered parts (from several pastes and printed with
different in-fill patterning and tip diameter) will be carried out by microstructure (optical
microscopy and electronic microscopy), mechanical properties, i.e. hardness, flexural strength
and toughness, density and shrinkage. The chemical characterization will be made by EDS
and the phases identification by XRD. The density and the presence of porosity will also be
determined in order to guarantee complete densification of the samples, free of internal
defects. The statistical distribution of the mechanical properties of the ceramic material is
flaw-controlled and does not follow a normal distribution. For that, it is assumed a heavy-
tailed distribution, i.e, Gumbel, Frechét or Weibull. The literature favors the use of Weibull
statistics and therefore this will be the approach used in this work following the
methodological orientation proposed by Quinn et al [97].

Task 5: Silicon nitride prototypes production and in-service performance evaluation

For predicting the behavior of the sintered parts in a real industrial environment, more
complex geometries will be printed, as for example cylinders with internal cooling channels,
since silicon nitride cutting tools with internal refrigerator channels are a new possible product
for Palbit S.A. The conditions that conferred the best results will be selected from task 2-4.
However, considering the geometric specifications of the tools, the paste formulation and
printing parameters should be adjusted. The fabricated prototypes will be characterized in
terms of CAD model reproducibility, quality of internal channels (geometry, size, minimum
diameter reached), surface quality, microstructure and mechanical properties. It is expected to
create new geometries and designs adjusted to the industry. Unlike wear, fatigue processes
are responsible for chipping the cutting edges. This type of damage starts with the
development of microcracks and their propagation, leading to the collapse of the tool. Cutting
conditions are dynamic (e.g. intermittent cutting) and are conducive to fatigue. In this way,
the fatigue of the prototypes will also be evaluated using common tests in the Palbit company.

20
 5. Preliminary work

Submitted Scientific Article

In the frame of the present PhD work, some experimental work was already made and
submitted in a scientific article to be considered for publication. The following items are the
main experimental procedures and the most important results attained.

5.1 Experimental procedure

Silicon nitride-based powder composition and Feedstock preparation
Silicon nitride (Si3N4, Grade M11, H.C Starck, Germany), alumina (Al2O3, Martoxid MR 70,
Huber Martinswerk, Germany) and yttrium oxide (Y2O3, ST-1028/98. H.C Starck, Germany),
in a proportion of 89.3 wt.%, 3.7 wt.% and 7.0 wt.%, respectively, were used as powder-based
composition [98] and milled for 8 h at 200 rpm in 2-propanol. After drying, the mixture
suffered a calcination at 600 ºC for 4 h, according to previous well-established procedures
[99–102]. This powder composition was hereafter defined as A-matrix. The particle size
distribution of the three ceramic powders and the final mixture was analyzed by a light-
scattering instrument (Particle Size Analyzer, Coulter LS 230, UK).
Dolapix A88 and Dolapix PC33 (both from Zschimmer & Schwarz, Germany) were selected
as dispersants, referred in literature as particularly effective in colloidal dispersion of silicon
nitride [18, 99, 103]. The deagglomeration efficiency was evaluated with 0.1, 0.2, 0.3 and 0.4
wt.%, based on total solids content, of Dolapix A88 and 0.2, 0.4 and 0.8 wt.% of Dolapix PC
on the viscosity of an A-matrix-based suspension containing 40 vol.%.
To ensure the proper stability of the slurries, carboxymethyl cellulose (CMC, 250 000 Mw,
Colorobia) was added to the suspensions as a binder/thickening agent. The suspensions were
characterized by rheological properties using a rotational rheometer (Kinexus Pro+, Netzsch,
Germany)
By using the dispersant selected and respective amount (Dolapix A88, 0.2 wt.%) aqueous-
based suspensions containing total solids loading in the range of 40-44 vol.% were then
prepared with a 3 wt.% diluted solution of carboxymethyl cellulose (CMC). Finally,
polyethyleneimine solution (PEI, Sigma-Aldrich-Merck, Germany, Mn ~1800 and Mw
~2000), was gradually added until a gel-like behavior is obtained, attaining a 0.06 wt.% (based
on solid amounts) of this additive.

Table 4 presents the solids loading of initial suspensions, amounts of additives added and the
solids loading in the final inks.

21
Table 4- Solids loading of A-Matrix initial suspensions, amounts of binders added and total solids
concentration in the final inks.

Initial Suspension Additives Final inks

(Solids loading) CMC PEI (Solids loading)
(vol.%) (wt.%) (wt.%) (vol.%)
40 0.2 0.06 36

42 0.2 0.06 38

44 0.3 0.06 39

5.1.1 Printing silicon nitride-based samples by direct ink writing and sintering
A robocasting equipment (EBDR-A32, 3D Inks, LLC, USA) was used to print cylindrical
samples with 20 mm diameter and 5 mm thickness. The ink extrusion was made at room
temperature, with a print velocity of 10 mm/s through a nozzle with an internal diameter of
410 µm. Figure 8 presents the CAD model with infill patterning used- all layers with filament
printed in the same direction and superimposed, already sustained by other authors [86]. After
printing, the samples were dried in a controlled humidity oven for 24 h and another 24 h at
room temperature.
In order to reduce the porosity in green state and evaluate its effect in the final properties,
some of the samples were submitted to cold isostatic pressing (CIP) for 15 minutes at 200
MPa (Autoclave Engineers, Erie, PA). This technique has been recently demonstrated to
improve the mechanical properties of AM parts [74]. After that, the de-binding cycle was
defined as 1 ⁰ C/min until 500 ⁰C during 1 hour at this temperature, with natural cooling. The
sintering process was carried out in a graphite furnace (Termolab, Águeda, Portugal) with a
controlled N2 atmosphere, slightly above atmospheric pressure, at 1750 ºC during 2 h [104].
The heating and cooling rates were 10 ºC/min. The samples were measured before and after
sintering to determine shrinkage.

22
 (b)

Figure 8- (a) CAD model of cylindrical samples and infill patterning used; (b) robocasting
printing process of A-matrix based paste.

5.1.2 Characterization of printed Si3N4-based samples

The printed and sintered samples fabricated by robocasting, with and without CIP, were
characterized in terms of structural and mechanical performance. The microstructure of
fractured samples, polished, and etched by CF4 plasma, was examined by scanning electron
microscopy (SEM, Hitachi SU70, Tokyo, Japan).
Vickers micro-hardness was measured in polished surfaces of the printed samples using 2 kgf,
during 10 seconds in a Wilson VH1102 microhardness tester (Buehler, Illinois USA) and were
submitted to a flexural strength test using the piston-on-three-ball at the constant rate of
applied load of 1 mm/min according to ISO 6872 (2015) [105].

5.2 Results and discussion

5.2.1 Raw materials and feedstock characterization for direct ink writing (DIW)
Silicon nitride powder has two particle populations centered around 0.3 µm and 2 µm, the
latter probably due to agglomeration, with a D50 of 1.13 µm, while yttria presents a D50 of
1.34 µm. Alumina is the raw materials powder that presents the largest particle sizes with a
D50 of around 2.8 µm.
After mixture and ball milling, the A-matrix composition presents the most representative
particles’ population with sizes less than 1 µm (centered around 0.5 µm), emphasizing the
milling effectiveness of this operation. A small particles’ population centered at ≈ 3 µm is less
23
representative and could be resultant to the larger alumina particles or agglomeration of some
fine particles.

The pastes’ preparation for robocasting started with the selection of the most appropriate
dispersant to obtain aqueous suspensions with high solids loading as low viscous as possible.
Figure 9 presents the viscosity versus shear rate for A-matrix suspensions in the presence of
different amounts of Dolapix PC 33 and Dolapix A 88, containing a total of 40 vol.% of solids.

a) b)

Figure 9- Viscosity versus shear rate of A-matrix suspensions with 40 vol.% solids in presence of (a)
0.2, 0.3 and 0.4 wt.% Dolapix PC 33 (D-PC33) and (b) 0.1, 0.2, 0.3 and 0.4 wt.% Dolapix A88 (D-
A88).

The suspensions containing 0.2 and 0.4 wt.% of Dolapix PC 33 present an accentuated shear
thickening behavior at shear rate values higher than 50 s-1, that tends to disappear when 0.8
wt.% of Dolapix PC33 is added [106]. This shear thickening behavior for higher shear rate
values is also visible in the suspension containing 0.1 wt.% of Dolapix A88. For higher
amounts of Dolapix A88 (0.2, 0.3 and 0.4 wt.%) all suspensions exhibit a shear thinning
behavior for all range of shear rates tested. Moreover, Dolapix A88 is the dispersant that
confers lower viscosity with lower added quantities when compared to Dolapix PC33.
According to these results, 0.2 wt.% of Dolapix A88 was selected for further studies.

Figure 10 (a) presents the flow curves of the suspensions containing 40, 42 and 44 vol.% of
A-matrix, with 0.2 wt.% of Dolapix A88, before and after CMC addition. In the absence of
CMC, all suspensions presented a shear thickening behavior that is highly pronounced as
solids loading increased. In fact, the suspensions only with deflocculant at low shear rates
appears to be fluid, but after a minimum stirring, the suspension offers a considerable
resistance, behaving like a solid (
Figure 10 b). The addition of CMC confers to all suspensions a shear thinning behavior and
an increase in the viscosity (
Figure 10 c), even if the solids concentration decreased (as presented in Table 4).
The rheological properties of the final inks are presented in Figure 11. For all A-matrix pastes
from different concentrated suspensions, the elastic behavior (G’) dominates over the viscous

24
one (G’’) predominating a solid-like behavior without significative changes for pastes with
different solids loading. The G’ stability along a high shear stress range (linear viscoelastic
region, LEVR) suggests that deposited paste rods will support the weight of subsequent layers
during printing process, keeping the mechanical integrity of the ceramic part.

a b)
)

c)

Figure 10- a) Flow curves of the A-matrix suspensions containing 40, 42 and 44 vol.% of solids in the
presence of 0.2 wt.% Dolapix A88, without and with carboxymethyl cellulose (CMC), (b) example of
a suspension with 44 vol.% with a shear thickening behavior and (c) same suspension after CMC
addition with shear thinning behavior.

25
Figure 11- Storage modulus (G’) and loss modulus (G’’) versus shear stress for A-matrix pastes
containing different amounts of solids (36, 38 and 39 vol.%).

Additionally, during the printing process it was perceptible that the printed parts tends to dry
very fast, highly pronounced for the pastes containing the highest solids loading in good
agreement with concerns from other authors [107, 108]. The option of using an oil bath to
avoid high drying rates was not taken into account, since the literature mentioned that oil can
be trapped between the filaments leading to void formation after burnout [86]. So, in order to
prevent nozzle clogging and cracks in the printed parts, it was crucial to maintain a high
humidity environment during the printing step, as well as a very slow drying process before
the CIP and the heating treatments.

5.2.2 Sintered Si3N4-based printed parts characterization.

Structural and mechanical properties
Table 5 presents the main results obtained with robocasting of the different developed pastes,
sintering of the samples and characterization.

Table 5- Properties of sintered A-Matrix samples obtained from pastes with 36, 38 and 39 vol.% of
solids, without and with cold isostatic pressure (CIP) after printing.

Relative Flexural Vickers

Solid Shrinkage
Density (%) strength Hardness
loading (%)
(MPa) (HV2)
36 vol.% 3,04 ± 0,04 92,91 ± 1,31 242 ± 6 1322 ± 35
WITHOUT
38 vol.% 3,13 ± 0,05 95,83 ± 1,19 371 ± 15 1388 ± 36
CIP
39 vol.% 3,14 ± 0,05 95,91 ± 1,81 427 ± 86 1407 ± 21
36 vol.% 3,19 ± 0,02 97,69 ± 0,57 321 ± 15 1402 ± 47
WITH CIP 38 vol.% 3,21 ± 0,04 98,04 ± 1,36 507 ± 100 1418 ± 20
39 vol.% 3,23 ± 0,01 98,67 ± 0,40 630 ± 41 1475 ± 25

26
It is possible to observe that CIP improves both properties of each solid load composition
specimens. Also, both relative density and micro-hardness rises as the solid load in the sourced
pastes increases. Relative density increases from an average of 92 % for parts obtained with
the paste having 36 vol.% of solids to an average of 96 % for the ones obtained with 39 vol.%
paste, in absence of CIP. Applying CIP, relative densities presented at least a 2 %
improvement for both parts obtained from 38 and 39 vol.% pastes. The highest relative density
improvement (around 5 %) was observed for the parts produced from the paste with 36 vol.%
solids. The highest relative density, 98.6 ± 1.3 % value was attained for the sample with 39
vol.% solids submitted to CIP. Samples with the same solids loading, without CIP, have an
average of 96 ± 1.4 % relative density.
The average hardness of the samples obtained for 36, 38 and 39 vol.% with CIP were 1402
(13.7 GPa), 1418 (13.9 GPa) and 1475 HV2 (14,5 GPa), while for the same compositions
without CIP were 1322 (12.9 GPa), 1388(13.6 GPa) and 1407 HV2 (13.8 GPa).
For parts obtained from the paste with the same solids loading, the ones submitted to CIP also
presents higher values of flexural strength, as expected. The average flexural strength of the
39 vol.% samples with CIP was 630 ± 41.02 MPa while the same composition without CIP
presents flexural strength values of 427.11 ± 86 MPa. It is important to mention that almost
all results presented a high variability inherent to the printing process. In fact, samples made
by AM have limited reproducibility caused by defects generated during the printing, such as
missing layers, filament extrusion deficiency, cracks resultant to the fast drying and poor green
mechanical resistance. So, the flexural strength results could be clarified by analyzing the
microstructure of the cross-section after the flexural test.
The samples processed without CIP fractured in a reduced number of parts, usually 2, as
shown in Figure 12 (a) and (b). The probability of origin of fracture in these samples are
highlighted with red circles and could be identified as drying cracks, missing filaments, and
interfilamentous pores. On the other hand, CIPed samples fractured on 3 or more parts, Figure
12 (c). In this case no macro-defects were visible. These fracture behaviors can be related with
the material’s intrinsic properties and the tensile stress distribution of the chosen flexural
strength test.

27
 250 µm

250 µm

250 µm

Figure 12- Surface fracture of samples with 39 vol.%, resulting from the flexural strength test.
Samples a) and b) were sintered as printed (without CIP) while sample c) was CIPed after printing.
Probable fracture origins are stressed with red circles, where: a) drying cracks and b) printing pattern.

The micrographs of the different samples with and without CIP are presented in Figure 13.The
microstructure shows long needle-shaped β-Si3N4 crystals embedded in the Y-Al-O matrix
containing intergranular, partially recrystallized, glassy phase, in accordance with a similar
material obtained using conventional processing methods [109].

28
 36 vol.%
38 vol.%
39 vol.% Without CIP With CIP

Figure 13- SEM morphology of non-CIPed and CIPed sintered Si3N4 printed parts after plasma
etching obtained with pastes pastes containing different amounts of solids (36, 38 and 39 vol.%).

For the best of authors knowledge, the values of flexural strength reported in the present work
(650 MPa) are higher than those presented by previous works related with the robocasting
processing technology for Si3N4 (350-552 MPa) [16, 18, 19]. However, since the mechanical
properties are usually related with multifactorial parameters, e.g. ink´s properties, sintering
additives, sintering procedure, the direct comparison between these data is not
straightforward.

29
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