Materials Letters: X 17 (2023) 100179

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Materials Letters: X
journal homepage: www.sciencedirect.com/journal/materials-letters-x

Effect of print direction on mechanical properties of 3D printed

polymer-derived ceramics and their precursors
Stephan A. Brinckmann a, Jason C. Young b, Ray S. Fertig III a, Carl P. Frick b, *
a
University of Wyoming, Mechanical Engineering Department, Laramie, WY, USA
b
Colorado School of Mines, Mechanical Engineering Department, Golden, CO, USA

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

Keywords: The use of engineering ceramics with intricate geometries is limited by manufacturing processes and lack ease of
Polymer-derived ceramics machinability of ceramics. Additive manufacturing of pre-ceramic polymers which are pyrolyzed into ceramics
Additive manufacturing after 3D printing has recently been used to circumvent traditional manufacturing processes creating ceramics
Mechanical characterization
with complex geometries, however, mechanical characterization is limited. Polymer-derived ceramics and their
Ceramics
Polymers
green-body precursors are printed using digital light projection 3D printing in two orientations (0◦ - and 90◦ - to
the build plate) and mechanically characterized. The results show that mechanical anisotropy exists both in the
green-body polymer samples where the 0◦ -samples are stronger and stiffer than their 90◦ -counterparts and the
final ceramics, where the stronger samples are fabricated at 90◦ despite isotropic hardness measurements.
Through the manufacturing process, it was noted that samples undergoing pyrolysis built in the 90◦ -orientation
have a pyrolysis survival rate of 94% whereas the 0◦ -samples showed a survival rate of 54%. The results suggest
that the build-direction of 3D printed green-bodies plays a role in both material manufacturing and mechanical
integrity of the final ceramic materials.

1. Introduction
Although additive manufacturing technology—often synonymous
with 3D printing—has been rapidly evolving, the vast majority of
printers continue to rely on polymer- or metal-based materials for
printing [1]. However, for applications in extreme environments that
require ceramic materials to withstand high temperature or corrosive
conditions, additive manufacturing options are limited. To-date,
spatially complex and custom ceramic parts have been difficult to ma­
chine and expensive to manufacture [2]. Combining ceramic materials
with additive manufacturing is an exciting prospect for introducing
complex, rapidly-manufactured, low-cost ceramics [3].
One method of 3D printing ceramics utilizes polymer-derived ce­
ramics (PDCs). PDCs can be pyrolyzed from a cured polymer, typically
with a Si-backbone, into Si-based ceramics [4]. Recently, near fully-
dense PDCs have been printed using commercially available vat pho­
topolymerization 3D printers into complex shapes not possible via
conventional ceramic manufacturing techniques[5]. Final ceramic
physical properties can differ significantly depending on precursor
chemistry and material processing [4]. Additionally, the maximum size
of PDCs is also inherently limited due to cracking during densification;
in general, PDC features larger than 500 µm require low heating rates for
successful pyrolysis [6]. As such, printed samples have a tendency to fail
during the pyrolysis process. Nonetheless, studies have collectively
demonstrated that for small, complex parts, printing of PDCs has shown
great promise.
The focus of these initial 3D printed PDC studies has been on
manipulating precursor chemistry in order to realize better dimensional
control and to increase ceramic yield. In-depth investigations into me­
chanical properties have only been explored in short-order [5,7]. This is
surprising as additively manufactured materials are known to exhibit
anisotropic mechanical properties. Additively manufactured polymer
tensile test specimens typically fail at lower stress when the interlayers
are perpendicular to the loading direction when compared to print
orientations that are parallel to the loading direction [8]. These often
weaker interlayers can act as a pre-determined crack paths for failure.
The goal of this study was to investigate mechanical anisotropy in 3D
printed PDC materials as to-date this has yet to be reported on.
2. Methods and materials
Fig. 1 describes the fabrication process. Poly(ethylene–glycol)-

* Corresponding author.
E-mail address: cfrick@mines.edu (C.P. Frick).

https://doi.org/10.1016/j.mlblux.2022.100179
Received 6 June 2022; Received in revised form 6 December 2022; Accepted 7 December 2022
Available online 10 December 2022
2590-1508/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
S.A. Brinckmann et al. Materials Letters: X 17 (2023) 100179

Fig. 1. Manufacturing of a pre-ceramic photopolymerizable siloxane resin is subjected to UV light in the form of DLP printing to generate 3D printed structures. The
green-body polymer is then pyrolyzed at 1000 ◦ C in argon atmosphere to a final amorphous SiOC ceramic.

Fig. 2. Mechanical results of the polymer tensile tests (A) representative stress–strain behavior, (B) ultimate-tensile strength, (C) elastic modulus, and (D) Vicker’s
hardness for the 0◦ - and 90◦ - print orientations. Mechanical results of the ceramic 3-point bend tests with the ceramic results showing (E) the 3-point bend stress-
displacement behavior of the post-pyrolysis samples, (F) resulting ultimate-bending strength, (G) apparent bending modulus, and (H) Vicker’s hardness for the 0◦ -
and 90◦ - print orientations.

diacrylate and VinylmethoxySiloxane were mixed with Igracure 819
(photoinitiator) and Irganox 1330 (free-radical scavenger) to create a
potopolymerizable siloxane-based resin. The resin was printed using an
Asiga Pico2HD digital light projection 3D printer and subsequently py­
rolyzed at 1000 ◦ C in an argon atmosphere to produce the final ceramic.
As previously investigated by the authors, the final ceramic yield was
measured be 36.9 % and was found to be amorphous SiOC, empirically
SiO1.1C6.5 with an average linear shrinkage of 42 % [9].
Mechanical tensile specimens were directly printed with desired
printing parameters and orientation in the form of either ASTM D638-14
Type IV dogbone shape for polymer samples or ASTM D790 3-point bend
test specimens for ceramics. For each test, 15 samples were printed in
either the 0◦ - or 90◦ -orientation to the build plate. Testing was per­
formed using a custom ADMET micro-tensile tester with a constant
displacement rate of 0.01 mm/s. All samples were tested to failure.
Hardness of the polymer green-bodies and final ceramics were
measured using a Buehler Micromet II Vicker’s digital microhardness
tester indented using a 1 kg load. Resulting corner-to-corner diagonals of
the Vicker’s indent were measured and used to calculate hardness.
Scanning electron microscopy (SEM) of the fracture surfaces was per­
formed on a FEI Quanta FEG 450 field emission scanning electron mi­
croscope operating at a voltage of 20 kV with a spot size of 3.0.
3. Results and discussion
When comparing the failure stresses of the 0◦ - and 90◦ -orientations
(Fig. 2A and B), the ultimate-tensile stress was much higher in the 0◦ -
orientation, 10.7 MPa ± 2.4 MPa, than in the 90◦ -orientation, 1.6 MPa
± 0.21 MPa. The elastic moduli measured 660 MPa ± 48 MPa for the 0◦ -
orientation and 610 MPa ± 14 MPa for the 90◦ -orientation, which in­
dicates that the modulus is not significantly affected by orientation (2C).
Vickers hardness was measured to be 2.98 HV ± 0.43 HV when indented
on any face of a green-body sample fabricated in the 90◦ -orientation,
and 2.79 HV ± 0.49 HV in the 0◦ -orientation (2D).
Ceramic 3-point bend samples were designated 0◦ - and 90◦ - relative
to the direction of maximum tension under bending. Comparing orien­
tations (Fig. 2E and F), the average bending failure stress was much
higher in the 90◦ -orientation, 33.7 MPa ± 9.1 MPa, than in the 0◦ -

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S.A. Brinckmann et al. Materials Letters: X 17 (2023) 100179

Fig. 3. Scanning electron microscope of failed polymer tensile samples fabricated in the (A) 0◦ - and (B) 90◦ - orientations and failed ceramic 3-point bend samples
fabricated in the(C) 0◦ - and (D) 90◦ - orientations.

Fig. 4. Post-pyrolysis ceramic 3-point bend samples (Left) and pyrolysis survival rates (Right) of 3-point bend specimens fabricated in the 0◦ - and 90◦ - orientations.

orientation, 13.6 MPa ± 6.3 MPa. Orientation does not appear to have a
significant effect on stiffness. The bending moduli measurements
showed 18 GPa ± 2.1 GPa for samples fabricated in the 0◦ -orientation
and 19 GPa ± 1.2 GPa for the 90◦ -orientation (2G). Like the modulus
values, indentation properties are also independent of the print-
direction (2H). An average hardness of 6.91 GPa ± 0.60 GPa was
measured when indented on any-side of the 90◦ -orientation samples and
7.02 GPa ± 0.30 GPa for the 0◦ -orientation.
Fracture surfaces of failed specimens were analyzed via SEM to
investigate obvious defects which could influence failure. Green-body
tensile samples printed in the 0◦ - and 90◦ -orientations both show that
the fracture is relatively flat. The 0◦ -samples, which show the distinct
print layers, fracture through the thickness of the polymer tensile sample
(Fig. 3A). The 90◦ -dogbones fracture directly along a single polymer
layer interface (3B). Similarly, the fracture of the ceramic 0◦ -specimens
are relatively flat overall (3C), with print-layers clearly visible. In the
90◦ -orientation, the fracture surface of 3-point bend tested ceramic
samples are smooth and occur along a print-interface (3D).
Because 3D printed PDCs can often fail during pyrolysis, the
orientation-dependent pyrolysis survival rate of these specimens was

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S.A. Brinckmann et al.
also investigated. Samples that were printed in the 90◦ -orientation had a
much higher probability of surviving pyrolysis without noticeable
cracking or warping (Fig. 4). Survival rates of 94 % for the samples built
in the 90◦ -direction was nearly twice that of the 0◦ -orientation at 55 %.
Failed samples often developed small cracks, typically in conjunction
with slightly warped post-pyrolysis geometry.
Orientation dependent anisotropy in the polymer tensile samples is
not surprising. Differences in polymers fabricated in the 0◦ and 90◦
orientation has been previously noted in vat photopolymerized poly­
mers [8]. In direct contrast to the polymer samples, the 90◦ -orientation
3D printed ceramics are stronger than their 0◦ -counterparts. The lower
failure stress of the 0◦ -specimens can be linked with manufacturing
defects created during the pyrolysis process. With the high frequency of
pyrolysis failure of the 0◦ -samples compared to the 90◦ , it is likely that
mechanical integrity of the samples is negatively impacted by defects
generated during pyrolysis due to inadequate outgassing of the volatile
species. The lack of hardness anisotropy also suggests the difference in
the ceramic between orientations is likely driven by critical defects
developed during pyrolysis.
4. Conclusions
A 3D printed siloxane-resin was used to manufacture 3-point bend
samples in a 0◦ - and 90◦ -orientation which were subsequently pyrolyzed
and tested. The results showed that overall, the 90◦ -orientation ceramics
proved stronger (33.7 MPa) than those printed in the 0◦ -orientation
(13.6 MPa), which is counter-intuitive with respect to similar anisotropy
of additively manufactured polymers where this effect is noted to be
opposite. However, survival rates when undergoing pyrolysis are also
lower in the 0◦ -orientation at 54 % when compared to the 94 % of 90◦ -
orientation samples. In addition, hardness values are orientation-
independent with a 0◦ - and 90◦ - hardness measured at 7.02 GPa and
6.91 GPa, respectively. These results suggest that there are more
pyrolysis-induced defects in the 0◦ -specimens leading to both a lower
ultimate-bending stress and survivability. Ultimately, additional studies
are needed to better print direction anisotropy and understand the
mechanisms of defect formation during pyrolysis in 3D printed PDCs.
CRediT authorship contribution statement
Stephan A. Brinckmann: Conceptualization, Methodology, Data
curation, Writing – original draft, Writing – review & editing. Jason C.
Young: Writing – review & editing. Ray S. Fertig: Supervision,
Materials Letters: X 17 (2023) 100179
Conceptualization, Writing – review & editing. Carl P. Frick: Supervi­
sion, Conceptualization, Writing – review & editing.
Declaration of Competing Interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Carl Frick reports financial support was provided by US Department of
Energy.
Data availability
Data will be made available on request.
Acknowledgements
The authors gratefully acknowledge funding from The Department of
Energy (DOE), Office of Fossil Energy, Advanced Turbines Program (DE-
FE0031758).
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