AM For Ceramic

REVIEW
DOI: 10.1002/adem.201400097
Additive Manufacturing of
Ceramic-Based Materials**
By Nahum Travitzky,* Alexander Bonet, Benjamin Dermeik, Tobias Fey,
Ina Filbert-Demut, Lorenz Schlier, Tobias Schlordt and Peter Greil
This paper offers a review of present achievements in the field of processing of ceramic-based
materials with complex geometry using the main additive manufacturing (AM) technologies. In
AM, the geometrical design of a desired ceramic-based component is combined with the materials
design. In this way, the fabrication times and the product costs of ceramic-based parts with required
properties can be substantially reduced. However, dimensional accuracy and surface finish still
remain crucial features in today’s AM due to the layer-by-layer formation of the parts. In spite of the
fact that significant progress has been made in the development of feedstock materials, the most
difficult limitations for AM technologies are the restrictions set by material selection for each AM
method and aspects considering the inner architectural design of the manufactured parts. Hence,
any future progress in the field of AM should be based on the improvement of the existing
technologies or, alternatively, the development of new approaches with an emphasis on parts
allowing the near-net formation of ceramic structures, while optimizing the design of new materials
and of the part architecture.
1. Introduction expansion of the use of advanced ceramics in key sectors.[1] It

is an incontrovertible fact that the wide industrial use of
The design and development of advanced ceramics for advanced ceramic materials depends on the technological
high-performance applications ranging from automotive to availability to fabricate near-net-shaped three-dimensional
aerospace, defense-oriented, energy, environmental, and ceramic-based parts with the required geometry. The latter is
biomedical applications is one of the most challenging tasks of great importance because the post-hard machining of
of modern engineering. Examples of current and future ceramics is time-consuming and an expensive process that
applications of advanced ceramics are given in Ref.[1] The generally requires diamond tools. Thus, in many cases, it
need for advanced ceramics primarily depends on the growth incurs up to 80% of the overall manufacturing costs of a
of end-use markets. On the other hand, technological ceramic product.[2] In addition, since for small-scale
innovations have continuously contributed to performance manufacturing and prototyping the expenses for models
and productivity improvements, which have stimulated the and molds are crucial factors in the production costs, it is
difficult to implement new designs quickly in test parts. The
*[*] PD Dr. N. Travitzky, A. Bonet, B. Dermeik, Dr. T. Fey inability of current technology-related methods to produce
I. Filbert-Demut, L. Schlier, Dr. T. Schlordt, complex-shaped ceramic-based parts with the desired com-
Prof. P. Greil positions, microstructures and properties directly from
Department of Materials Science, Glass and Ceramics, computer aided design (CAD) files or data obtained using
University of Erlangen-Nuremberg, Martensstr. 5, 91058 reverse engineering methods including scanners and com-
Erlangen, Germany puter tomographs (CT or m-CT) without hard tooling, dies or
E-mail: nahum.travitzky@ww.uni-erlangen.de molds has led to novel techniques such as additive
[**] The authors thank the Deutsche Forschungsgemeinschaft (generative) manufacturing (AM), solid freeforming (SFF),
(DFG) and German Federation of Industrial Research rapid prototyping (RP), rapid manufacturing (RM), rapid
Associations “Otto von Guericke” e.V. (AiF) for financial tooling (RT), layer manufacturing (LM), and direct digital
support. manufacturing (DDM) that are becoming increasingly more
ADVANCED ENGINEERING MATERIALS 2014,

DOI: 10.1002/adem.201400097 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com 1
N. Travitzky et al./Additive Manufacturing of Ceramic-Based Materials
REVIEW
Fig. 1. Classification of AM processes according to dimensional order, commercial availability, state of aggregation of their starting material, and the type of layer formation.
important processing techniques in which three-dimensional software to define a large number of layers. These are closely
objects are assembled by point, line or planar addition of spaced parallel contours that are subsequently registered,
material without the use of tooling. Confining surfaces, such stacked and fused together by the solid modeling apparatus,
as mold or die walls, are absent. The shape is built by adding through curing, binding, depositing and sintering.[5,6] In the
rather than subtracting material.[3] The basic unit operations 1990s, H. Koukka presented the whole family tree of major
and the layered assembly strategy have long histories. The additive fabrication technologies (commercialized, experi-
early roots of additive technology can be traced to at least two mental and/or patented – according to applied fabrication
technical areas: topography (since 1892) and photosculpture technique and nature (phase), and/or form of build material),
(since the 1870s). An early chronological timeline of AM is which is a compendium of those methods that were, are and
given in Ref.[4] Since the early 1980s, automation in this area are yet to be.[7] The physical size of the generated products
has continuously improved in parallel with the expansion of may range from nano/microscopic to macroscopic and even
the data handling capacity of personal computers.[3,5] In AM to entire buildings.[8] Figure 1 shows the classification of
methods, a computer is used for: (a) processing the commercialized AM processes used for the fabrication of
geometrical information and (b) controlling the machinery ceramic-based materials according to dimensional order,
assembling the physical parts layer by layer. For instance, a commercial availability, state of aggregation of their starting
CAD model, usually a solid or surface model, is sliced by the material and the type of layer formation.
A full classification of AM is given, for example, in the
German production process standard (DIN8580) and
especially in the German archetyping standard
(DIN8581). Most of these techniques have been commer-
cialized for the fabrication of polymer and metal parts.
However, up to now there have only been few systems
available for the production of functional-quality ceramic
components. This is hindering the introduction of new parts
because staggering tooling costs frequently prohibit the
generation of functional-quality ceramic-based bodies with
complex geometry and hence their subsequent application.
For this reason, research has been done during the last
several years to develop AM methods that allow the
fabrication of ceramic components. In general, already
existing AM techniques have been adapted for the
processing of ceramic containing feedstock.
Several excellent review papers and books dedicated to
AM have been written in the last two decades. However, most

2 http://www.aem-journal.com © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adem.201400097
REVIEW
of these publications focused on AM, which was solely between the nozzle and the previously deposited layers.[35]
applied for the fabrication of design and display models as Often an ink additive is used to prevent drying and clogging
well as for limited-lot production, primarily on the basis of of the nozzles.[28,36] The DIP method is considered the only
polymers and metals. A recent review paper on the processing method among all additive processing techniques that is able
of ceramic-based composites only briefly considered an to produce dense ceramic bodies without a post-processing
application of AM methods in ceramic processing.[9] The treatment.[19,30,37]
latest review paper on AM does include ceramics next to Oezkol et al.[22] successfully fabricated dental prostheses
polymers and metals; the main focus, however, is on the (Figure 2a) from zirconia inks using the DIP method by
general consideration of this technology, the materials and the depositing a supportive carbon ink prior to the ceramic ink.
applications.[10] To our knowledge, the only review paper Flexural strength determination according to the four-point
with an emphasis on ceramic materials that attempts to set out bending test revealed higher performance with DIP compo-
the taxonomy of AM methods in a historical context, thereby nents than with slip-cast samples. A boehmite sol in ceramic
disentangling the multiplicity of process names that have inks (see Ebert et al.[36]) prevented agglomeration of the ZrO2
arisen over the past two decades, was presented in 2003.[3] particles and enhanced the green body strength of dental
Therefore, the aim of the present work is to review the restorations. The DIP technique has also been applied to create
achievements in the field of ceramic processing with a main parts from wax-based alumina inks,[24–26] demonstrating the
focus on commercialized AM methods. suitability of low-melting point waxes for hot-melt ink-jet
printing. A functionally graded composite was printed from
zirconia and alumina inks by Mott and Evans,[23] whereas the
2. Three-Dimensional Printing (3DP)
one-dimensional gradient was comparable to the predicted
Three-dimensional printing is a promising method of composition. Alcohol-based zirconia inks were also applied to
producing accurate parts with complex geometries that offers manufacture complex-shaped geometries, which may be used
countless potential applications such as tissue engineering as miniature heat exchangers.[38,39] Besides creating dense
scaffolds and functional and advanced ceramics. There are parts, the DIP technique can be used as a cost-effective and
several printing methods on the market today, with the majority flexible way to manufacture coatings and devices from
based on ink-jet technology. The three-dimensional printing functional ceramics. Dielectric coatings were printed from
technique can be divided into direct printing techniques inks of BaTiO3 nanopowders[40,41] or were derived from
(DIP)[11–16] and indirect printing techniques.[17] DIP directly printed layers of titania sol and barium salts solutions[42];
deposit a well-dispersed ceramic suspension via the injection patterned TiO2 films with a height of 420 nm were obtained
nozzle, for example.[18] This technique has a continuous[11–13] from precursor solutions, without any masking and etching
and non-continuous approach as drop-on-demand (DoD).[14–16] processes.[43] Anatase thin films with a thickness of 130 nm to
A continuous ink-jet system uses droplets, which are deposited 1 mm were derived from micro-emulsion inks. It was shown
onto the printing substrate. Residual droplets are collected and that they possess hydrophilic properties, which can be
reused. In contrast, the nozzle position in a DoD-printer controls adapted for production of self-cleaning glasses.[44] Lejeune
the destination of the droplets, which are generated only when et al.[37] fabricated micro-pillar arrays (depicted in Figure 2c)
required.[19] The DIP methods combines fast and efficient from aqueous anatase and lead zirconium titanate (PZT) inks.
manufacturing of complex-shaped ceramic components with The diameter and height of pillars were controlled by
precise contours and excellent surface quality. Since the adjusting the printing conditions and properties of the
components are built layer by layer, bodies featuring cavities ceramic suspension. Suspensions of PZT powders in a
and overhangs are easy to produce. The use of supportive methylethyl ketone/ethanol[45] and paraffin/oil mixtures[46]
structures that can be removed after printing is therefore highly have also been prepared, demonstrating the suitability for
recommended.[20–22] In addition, DIP allows microstructure ink-jet printing. Bathurst and Kim[47] printed a piezoelectric
tailoring through blending and diluting the ceramic suspen- micro-machined transducer from PZT sol–gel inks. The
sions, leading to a graded composition of the printed body.[23] possibility of manufacturing coatings from electroceramics
The ceramic inks are typically prepared according to two using DIP was effectively demonstrated by printing
methods: using wax-based inks, which are deposited in hot- La0.7Sr0.3MnO3- and YBa2Cu3O7 x-based inks.[48]
melted state and solidify on a cold substrate,[24–26] or using The indirect printing technique is the most widely used
ceramic suspensions, which dry through evaporation of the method for commercial applications. Parts are manufactured
liquid.[27,28] Reis et al.[29] claimed that loaded wax containing up by distributing a binder liquid on a powder layer. It was
to 45 vol% of particles can be successfully ink-jet printed, developed by Sachs in 1992[17] and was initially used for
whereas the maximum solid content reported for an aqueous manufacturing prototypes and casting molds. The 3DP
suspension amounted27 vol%.[30] method can create parts with geometries of any complexity,
The accuracy of the dimensional resolution is not only including undercuts, overhangs and internal volumes, from
affected by the ink parameters (solid content, particle size, any powder material[6] without any additional support
viscosity[31–34]), but also by the extrusion parameters such as structures thanks to the powder bed. One of the major
the extrusion rate, nozzle travel speed and the distance advantages of this method is the high degree of geometric

DOI: 10.1002/adem.201400097 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.aem-journal.com 3
REVIEW
Fig. 2. Exemplary ceramic structures, fabricated with direct (a–c) and indirect (e–f) printing techniques: (a) dental restoration,[22] (b) impeller,[21] (c) micro-pillar array,[37]
(d) bone implant,[82] (e) macrocellular structures with variable ligament lengths.[62,63]
independence in the parts that can be produced.[6,49] The could reduce the porosity to 19 vol%.[59] Powder bed
remarkably high speed of 3DP is based on the inkjet principle stability can be optimized by moistening the powder during
and on the fact that no phase change of material is involved printing, resulting in enhanced surface roughness and
during the building process. Consequently, the combination geometric accuracy of the specimens.[60] Butscher et al.[56]
of numerous potential materials and low-cost equipment conducted a comprehensive study to relate the powder
together with outstanding speed means that 3DP offers great properties to printability. He quantified the optimal powder
perspectives for the future. Since dimensional accuracy is parameters such as the particle size (20–35 mm), compaction
directly influenced by material properties (particle size, rate rTapped/rBulk (1.3–1.4), flowability ffc, defined as the ratio
pourability, wetting behavior) as well as process parameters of consolidation stress s1 and the compression strength sc
(nominal dimensions, build orientation), the 3DP technique (5–7), and powder bed surface roughness (10–25 mm). The
still has some precision range compared to other RP methods. need for at least one post-processing step (cold-isostatic
Fine powders produce a smoother surface, yet become pressing,[61] infiltration with preceramic polymers[62,63] or
difficult to spread thoroughly on the working area. However, liquid metals,[51,64] chemical vapor infiltration,[65] and sinter-
the application of spray-dried[50] or freeze-dried[51–55] gran- ing[66,67]) reduces the productivity of three-dimensional
ules allows the use of fine sinter active particles. The higher printing methods, so several approaches exist to increase
the pourability of the powder, the thinner the layers are that the green density. It was observed that implementation of
are built by the leveling roller and, hence, the higher the binder-coated particles effectively improves the green and
resolution of the printed body. It was shown that the sintered strengths.[68]
wettability and pourability of powders can be sufficiently One of the main application fields of 3D printed parts is
improved through plasma treatment.[56] Plasma-enhanced artificial scaffolds from biocompatible ceramic materials such
chemical vapor deposition (PECVD) generates SiOx nano- as hydroxyapatite (HA) and calcium phosphates (CP). The in
particles on the surface of the substrate powder, which vivo observations of bone repair scaffolds from HA indicated
increase the distance between the powder grains and reduce that the bone growth was enhanced by the scaffold geometry,
the Van der Waals forces.[57] The high porosity amount of porosity and surface properties.[69,70] Seitz et al.[71] determined
40 vol% after printing is caused by the packing density of the the mechanical compression of similar scaffolds and recog-
distributed powder.[58] In addition, the porosity is affected by nized that the values are comparable with human bone tissue.
maximized layer thickness: minimization of layer height Will et al.[72] varied the porosity of printed samples from 30 to

REVIEW
65% by implementing different mixtures of coarse and fine that the decreasing fracture of coarser Si particles in the
HA powders. Fierz et al.[50] used sprayed-dried porous HA starting powder positively influenced the porosity of the
granules to create nano and macroporous scaffolds. A HA/ printed objects.
bioactive glass-ceramic composite was fabricated by Winkel
et al.[67] Custom-made specimens were also fabricated from
3. Selective Laser Sintering (SLS)
tricalcium phosphate (TCP)[56,60,73–77] or combined with
bioactive glass,[78] demonstrating their potential use as Selective laser sintering was developed by Carl R. Deckard
implants for bone replacement applications. Scaffolds with and Joseph J. Beaman in the 1980s at the University of
a designed macroporosity were printed from submicron TCP Texas.[87] It is a process in which particles of a powder bed are
powders with a layer thickness of 20 mm by Ref.[79] It was selectively fused together with a laser beam based on the
observed that printed bodies from calcium polyphosphate/ CAD/CAM data of the building part. The CAD/CAM model
polyvinyl alcohol mixtures showed higher compressive is sliced into layers with thicknesses typically in the 100 mm
strength compared to conventionally sintered samples of range, depending on the material used and its interaction with
equivalent porosity.[80] Bodies printed from b-TCP powders the laser beam, and the part is built up layer by layer. This
and phosphoric acid as a binder exhibited higher resolution enables fabrication of very complex-shaped parts, which are
and higher mechanical performance than samples fabricated not reproducible using other shaping processes. The first
with commonly used organic binder systems.[81] Khalyfa fabricated parts produced by means of SLS were from plastic,
et al.[82] obtained higher compression strength of polymer- but basically any materials available in powder form could be
infiltrated 3D printed tetracalcium phosphate specimens than used. Thermoplastic materials are predestined for SLS due to
of sintered specimens due to their lower porosity. Calcium their low melting point. Low-melting metals also satisfy the
aluminate cement, another biocompatible ceramic material, requirements for this process. In the case of thermoplastics
was used to create a two-piece model for bone reconstruction and low-melting metals, where densification is due to local
with 3DP.[83] melting, the term selective laser melting (SLM) is often used
The possibility of implementing direct and indirect instead of SLS. Especially challenging is the use of materials
printing methods in the manufacturing of parts from with high melting points such as high-melting metals and
structural ceramics is still being actively explored. Sun ceramics. Typically, densification of these materials is a solid-
et al.[61] fabricated complex-shaped objects from pre-coated state diffusion dominated process requiring high temper-
Ti3SiC2 powder. 3D printed samples with 10% binder atures and time to achieve acceptable densities. Another
concentration were subsequently cold-isostatically pressed problem is the induced thermal stresses during SLS due to
and sintered. He observed a significant influence of the cold- high heating and cooling rates. Because of the limited thermal
isostatic pressing on the theoretical density of sintered parts shock resistance of ceramic materials, thermal stresses during
compared to sintering alone. 3D printed Si3N4/dextrin bodies SLS led to crack formation in sintered parts. Wilkes[88]
with a porosity of over 70% were densified (to 60% of discovered that powder bed preheating can reduce thermal
theoretical density) by means of pressureless sintering and stresses and thus crack formation in ceramic parts produced
chemical vapor infiltration.[65] Highly-loaded aqueous silicon using SLS. Despite known limitations in densification process
nitride ink was developed[84] and DIP was demonstrated on during direct SLS due to short interaction time between the
an example of a gearwheel.[85] laser and the material, the ceramic community showed
Several research groups have intensively investigated the interest in the SLS process owing to the possibility to fabricate
potential of manufacturing intermetallic/ceramic composites complex-shaped parts that cannot be produced using
using a near-net-shape fabrication process involving infiltra- traditional ceramic shaping processes.
tion of porous preforms fabricated by means of 3DP. Yin et al.
applied agglomerated powders[86] and freeze-dried gran-
3.1. Direct SLS
ules[53,54] from TiC/TiO2/dextrin mixtures with varying
blending ratios. Although the particle size of the feedstocks There are very few works on direct laser sintering of
was comparable, the use of freeze-dried granules reduced the ceramics. Gureev et al.[89] investigated direct SLS of
porosity of printed objects from 65% to 55%. It was shown that stoichiometric mixtures of PbO, ZrO2, and TiO2 for synthesis
infiltration with liquid melts is strongly favored by a bimodal of PZT ceramics. They achieved a high porous structure with
pore structure in printed objects.[55] Printing of macrocellular a low density of about 20% of theoretical density. Bertrand
combustion reactors from 82 wt% SiC and 18 wt% dextrin was et al.[90] fabricated ceramic parts from pure zirconia (YSZ)
performed in a 3D printer with an average layer thickness of powder by direct laser sintering. They found that powder
90 mm. The green bodies were infiltrated with preceramic bed density, which is a function of powder size and shape,
polymer, pyrolyzed and filled with liquid silicon. The has a significant influence on the SLS process. The higher the
structure, which was metalized for electrical contact, is density of the powder bed, the higher the density of the
illustrated in Figure 2e. SiSiC lattice truss structures with ceramic can be achieved. Figure 3(1) shows some sintered
variable ligament lengths (see Figure 2f) with Si volume YSZ parts. It can be seen that fabrication of YSZ ceramic parts
ranging from 8 to 82% were fabricated by Ref.[63] It was shown by means of direct SLS is generally possible, but these parts

REVIEW
Fig. 3. (1) YSZ parts from direct SLS.[90] (a) CAD model, (b) sintered part, (c) YSZ cubic from SLS process, and (d) microstructure of the surface of the cubic; (2) Al2O3 from
direct SLS,[92] (a) laser sintered powder bed with J 8 J mm 2 and (b) with J 16 J mm 2. SEM micrographs of sintered alumina ceramic: (a) surface and (b) cross-section.
have a rough surface and porous structure. Achieved Fe2O3–Al2O3–SiO2, and Na2O–Al2O3–SiO2, which result from
densities were in the range of 56%. These two examples the impurities; 2) liquid-phase sintering allowing the liquid
give a good representation of the latest achievable qualities phase to spread; 3) liquid-solid phase bonding and sintering
of ceramics fabricated using direct selective laser sintering of during the period of cooling after laser irradiation. Gahler and
powder beds in which densification is due to solid-state Heinrich[94] described high densification of Al2O3–SiO2 slurry
diffusion processes. deposited layer by using a doctor blade, like in tape casting.
In order to increase powder bed density, the powder could Sintered parts had smooth surfaces and densities of up to 92%
be deposited in slurry form instead of a dry powder layer. due to liquid-phase formation of SiO2. L€ oschau et al.[95] also
Waetjen et al.[91] investigated slurry deposition by means of an achieved high densities for direct laser sintering of SiC. SiC
airbrush for direct SLS of alumina and zirconia parts. It was provides two distinct benefits for direct SLS. On the one hand,
possible to generate dense powder beds with densities of up high energy input can lead to partial oxidation of SiC to SiO2,
to 98% using conventional sintering in a furnace at 1500 °C for which acts as binder and provides liquid phase sintering. On
2 h. However, selective laser sintering of these powder beds the other hand, it can be infiltrated in a post-processing step
was not possible, which was ascribed to the lack of the liquid by Si forming dense Si/SiC. Moreover, infiltration with a
phase. Wu et al.[92] used aerosol assisted spray deposition of carbon compound can be used to increase the SiC:Si ratio by
alumina suspensions to generate smooth powder beds for formation of secondary SiC. Other groups tried to overcome
direct SLS. To investigate the influence of laser sintering the problem of poor densification of direct laser sintered
parameters such as laser power P [W], scanning speed ceramics by combining the SLS process with self-propagating
V [mm s 1] and laser beam size D [mm], they used the laser high-temperature synthesis (SHS). Slocombe[96] used the high
energy density J [J mm 2], which is defined as J ¼ P/V D. exothermic redox-reaction of TiO2, Al and C to synthesize
They found that with increasing laser energy density J the TiC–Al2O3 composite ceramic. The raw materials were mixed
densification of the powder bed increased, too. Full densifi- together in powder form and placed onto the building
cation was achieved for laser energy density J ¼ 8.5 J mm 2. platform of the SLS apparatus. Activation energy for the SHS
SEM analysis of the microstructure of sintered samples (see reaction was induced by the laser. If the energy input by the
Figure 3(2)) showed spherical grains with a smooth surface, laser was high enough, the redox-reaction could be pushed
which is an indication for liquid-phase formation during the on. Synthesized samples where highly porous and swollen
sintering process. Hence, no low-melting binder phase was compared to the primary scanning area. Fifty percent
added; the formation of the liquid phase was believed to be compaction of the powder bed was shown to reduce the
attributed to impurities in the starting alumina powder porosity and swelling effect due to dilution of the propagation
(Na2O, SiO2, Fe2O3, CaO, MgO). They explained the sintering wave during SHS reaction. It is assumed that further
process in three stages (described elsewhere[93]): 1) initial optimization of the density and homogeneity of the powder
sintering up to a eutectic formation of the liquid phase. The bed could lead to further reduction of porosity and facilitate
eutectic phase systems include Al2O3–SiO2, CaO–Al2O3–SiO2, reaction control.

REVIEW
3.2. Indirect SLS the low green density and the inhomogeneous microstructure.
To increase the green density, and thus the sintered density,
Since not all ceramics include or form a liquid phase, low- the green parts were infiltrated (pressure assisted) with an
melting binders could be additionally added. With this alumina suspension and/or warm isostatic pressed. Infiltra-
method primary particles are bonded through the binder tion was done with a pressure of up to 13 MPa, thereby
phase and not directly, so the process is called indirect achieving green density of 54% and sintered density of 64%.
selective laser sintering. After SLS, a post heat treatment (e.g., However, a gradient of large isolated pores was observed on
in a furnace) is needed for full densification of the produced cross-sectioned sintered parts, with a lower density core and a
parts. A distinction can be made between two groups of higher density edge (see Figure 4(2)). Warm isostatic pressing
binders: organic and inorganic. Thermoplastics are used as was carried out at 135 °C and 64 MPa for 5 min. Thus, green
organic binders. Deckers[97] used polyamide (PA) as the density of 93% and sintered density of 89% could be achieved.
binder phase for indirect SLS of alumina parts. Alumina and Combination of pressure-assisted infiltration and warm
PA powder (22 wt%) were mixed together in a ball mill. isostatic pressing leads to green densities of 83% and sintered
Powder bed was pre-heated to temperatures slightly below densities of 88%, comparable to warm isostatic pressed
the melting point of PA (Tm ¼ 179 °C). SLS was performed samples.
under N2 atmosphere to prevent oxidation of PA. It was found Tang et al.[99] used a slurry-based indirect SLS process to
that specific laser energy is required to achieve manageable fabricate high-density alumina ceramics. At first, alumina
green parts. Energy that is too low leads to fragile parts, and particles were coated with water-insoluble semi-crystalline
energy that is too high to polymer degradation. Due to low PVA. Then a suspension of coated alumina and water-soluble
powder bed density, the sintered part density that can be PVA as a binder was created. The suspension was deposited
achieved is limited. In order to achieve higher green densities, layer by layer using a doctor blade and SLS was performed by
the laser-sintered samples were cold isostatic pressed for varying laser power and scanning speed. In accordance with
1 min at 200 MPa. This made it possible to double the green other results, strong green parts were fabricated only under
density. After cold isostatic pressing the samples were certain SLS parameters. Energy density that is too low leads to
debinded and finally sintered in a furnace at 1600 °C. low green part strength and too high energy to evaporation of
Depending on sintering temperature and time, densities of the binder phase. Green parts with 57% of theoretical density
up to 92% of theoretical density could be achieved. Shahzad were fabricated using suitable laser scanning parameters.
et al.[98] used polypropylene (PP) microspheres, produced via After sintering this green parts at 1600 °C for 2 h, ceramics
thermally induced phase separation, as a binder phase. The with 98% density could be achieved. This high sinter density
powder bed was again pre-heated to temperatures slightly was ascribed to high dispersion and homogeneity of the
below the melting point of PP (Tm ¼ 149 °C) and SLS was slurry-based powder bed. Shahzad et al.[100] investigated
performed under N2 atmosphere. SLS sintered and post- indirect SLS of Y-TZP (yttrium stabilized tetragonal zirconia
processed parts were sintered in a furnace at 1600 °C for 2 h. phase) using the same procedure described above for indirect
Green parts had a density of 29–34% of theoretical density and SLS of alumina.[98] Green density in SLS sintered parts was
a sintered density of 39%. The reason for the low density was 36% of theoretical density and could be increased to 45%
Fig. 4. (1) SEM of the green samples produced by SLS (a), SLS þ PI (pressure-assisted infiltration) (b), SLS þ WIP (warm isostatic pressing) (c) and SLS þ PI þ WIP. (2) SEM of
cross-sectioned sintered samples produced by SLS (a), SLS þ PI (b), SLS þ WIP (c and e) and SLS þ PI þ WIP (d and f).[98]

REVIEW
through pressure-assisted infiltration and up to 90% through material systems are biocompatible and/or bioactive and
warm isostatic pressing. Sintered density without post- designated for biomedical applications that require biocom-
processing was 32%, with infiltration 54%, and with warm patibility of materials and complex shapes of products as key
isostatic pressing 92%. A combination of pressure-assisted mechanical properties. Latest developments in the field of SLS
infiltration and warm isostatic pressing leads to a sintered were adjusted to enhance the resolution of produced parts
density of 85%. These results are comparable to those from about one hundred microns to a few tens of micrometers.
reported for alumina.[98] Friedel et al.[101] used a modified This was the development of selective laser micro sinter-
SLS method to produce ceramic parts called selective laser ing.[117,118] To reach the intended resolution, submicron
curing (SLC). The starting materials (all in powder form) were ceramic powder and near infrared lasers with a wavelength
polymethylsilsesquioxan (PMS), as a preceramic precursor, of about 1 mm were used. In addition to the known problems
and SiC as an inert filler. PMS has a melting point of 60 °C of SLS of ceramics, poor absorption of ceramics in the near
and undergoes a curing process when heated up to 150– infrared wavelength spectra also accrued.
250 °C. Dry powders were mixed by means of ball-milling Summing up works done on SLS of ceramics, it can be seen
with a different SiC amount (40, 50, and 60 vol%). SLS was that densification by solid-state diffusion is not yet sufficient
performed with different laser powers and scanning speeds. due to the short interaction time between laser and material to
During the SLS process, laser-irradiating cures the PMS get adequate densities of SLS produced parts. High densities
selectively according to the CAD model. Green part was could be reached only using the liquid phase assisted
pyrolized in flowing Ar atmosphere in three steps. At first at sintering process. The liquid phase can be formed directly
220 °C for complete curing, then at 500 °C for release of gases, via the used material or additionally added in the form of a
followed by further heating up to 1200 °C for formation of binder.
stable oxycarbide ceramic residue. Liquid silicon infiltration
was performed in a vacuum at 1500 °C. While energy density
4. 3D Extrusion Freeforming of Ceramics (EFF)
that is too low results in insufficient melting and curing of the
polymer, density that is too high leads to melting of adjacent Extrusion freeforming of ceramics is an AM technology
areas in the powder bed, thereby limiting the accuracy of the based on the continuous deposition of ceramic loaded paste or
laser-cured part. Green density of up to 60% could be achieved preceramic precursor[119] extrudates in a layerwise fashion to
through accurate adjustment of SLC parameters. Pyrolysis of build up 3D structures.[120,121] A variety of synonyms exist that
green samples leads to shrinkage of about 3% of the samples. may lead to confusion. For instance, Fused deposition
Despite the shrinkage that occurs, porosity is increased due to modeling, which was modified in order to fabricate ceramics,
volume shrinkage of PMS, which is roughly 50%. Thus, the is often abbreviated FDC.[122]
maximum density of pyrolized samples that could be Other synonyms regarding these technologies that usually
achieved was 50%. XRD and SEM results of pyrolized do not mean FDC include: Extrusion Freeform Fabrication
samples showed an amorphous Si–O–C matrix with well- (EFF),[123] Aqueous Based Extrusion Fabrication (ABEF),[124]
dispersed crystalline SiC particles. Infiltration with liquid Filament Based Writing (FBW), Freeze Extrusion
silicon results in fully dense samples. Further-
more, the Si–O–C matrix disappeared during
infiltration and could no longer be detected. It
is assumed that the Si–O–C matrix undergoes
carbothermal reduction, which occurs above
1300 °C. As a consequence, the amount of
infiltrated silicon equals not only the amount
of porosity (50%) but also the amount of
oxycarbide (15%).
Inorganic binders for indirect SLS are
typically metal phosphates,[102] metal sili-
cates,[103] and metal borides.[104,105] The work-
ing principle is the same as for organic
binders, but one must consider that inorganic
binders cannot be burnt out and thus remain
as a secondary phase in the final product. A lot
of work has been done on ceramic composite
materials. Examples include ceramic-glass
composites[106–111] and ceramic-polymer com-
posites.[112–116] Here, the low-melting glass/
polymer provides densification due to the
liquid phase formation. Most of these studied Fig. 5. SiC grid structures made by robocasting.[186]

REVIEW
Fabrication/Freeze-Form Extrusion Fabrication (FEF),[125–
127]
Direct Ink Writing (DIW),[120] Slurry Deposition,[128]
Dispense Plotting,[129] Bioplotting,[130] Rapid Prototyping
Robotic Dispensing (RPRD), Microextrusion Freeforming
(MF), Multiphase Jet Solidification (MJS),[131] 3D Fiber
Deposition (3DFD),[132] and Robocasting (RC).[133] These
synonyms exhibit mostly minor deviations regarding the
process details. To avoid confusion, this review mainly refers
to three terms: FDC (a liquefied ceramic–polymer suspen-
sion, similar to an injection molding feedstock, is deposited
onto a substrate), RC (a suspension or colloidal gel is
deposited at ambient temperature), and FEF (a suspension or
colloidal gel is deposited and frozen on the cooled substrate).
The term EFF will be used for the whole range of these
technologies. An important distinction between all these
technologies is the method of shape retention.[10] There are
phase changing techniques such as FDC, MJS, and FEF,
which utilize a liquid suspension or precursor that is
“frozen” upon deposition to maintain its shape, which
may mean either crystallization of the liquid phase, a glass
transition or a mixture of both. A method without a phase
transition is the evaporation of the solvent to induce
dilatancy of the suspension to maintain the shape; this
method is utilized by RC.[133] The latter technique may also
utilize reversible gel feedstock properties of coagulated Fig. 6. Variety of transducers made by FDC: (a) 10 10 tube array; (b) bellows;
colloidal suspensions whose rheological properties often (c) spiral; (d) curved transducer; (e) telescoping; (f) radial actuators made by FDC.[169]
solely serve as the shape retaining property. Another hybrid

between FDM and sol-gel technique not mainly applied to
ceramics (only HA and TCP, according to the manufactur- 4.1. A Brief History of Filament-Based Writing of
er[130]) is used by bioplotting: a heated thermoreversible Ceramics
hydrogel is deposited into a cold bath to induce a sol–gel
transition.[134] Furthermore, shape retention can be achieved The principle of EFF technologies was actually applied to
through the usage of UV-curable inks.[135,136] Another ceramics centuries ago when ceramic items were formed by
significant distinction of the techniques described here is joining clay strands manually to make containers and artistic
how the extruders are fed with material: among FDC, a solid items.[143] However, the deposition of ceramic materials with
feedstock wire from spools is continuously fed into the robotic devices was first applied in the 1990s. A first
feedstock-dispenser (called liquefier) and also acts as a publication reporting of RC, developed at Sandia National
piston to produce the extrusion force.[137] In other cases, Labs in 1996 (U.S. Patent 6,027,326), was published by
granulate is fed into a screw extruder,[138] whereas RC and Cesarano et al.[128] In original RC, a highly solid-loaded
FEF require a paste (or colloidal gel/ink) reservoir, which aqueous slurry close to dilatancy is cast onto a heated plate to
may be directly connected to an extrusion nozzle (see induce a transition from a flowable slurry to a dilatant mass by
Figure 6) or connected to a progressive cavity pump[139,140] drying to maintain the shape.[133,144] Further development led
on which the nozzle is attached. MJS may be fed by different to utilizing colloidal gels with different rheological properties,
feedstocks, such as powder, pellets, or bars (Table 1).[141] which could retain the shape without drying.[145] These
Table 1. Classification of the most important EFF techniques by method of shape retention.[119,123,124,130,137,138,140–142]
Technique Robocasting Freeze-extrusion fabrication Fused deposition of ceramics
Temperatures RT, occasionally heated plate Below freezing point of solvent 140–185 °C (FDC), 220 °C (MJS)
Writing velocities (mm s 1) <150 Tens of mm s 1 Tens of mm s 1
Extrudate diameter [mm] 30 to >2000 (particle loaded), <1 (precursor) 600 mm >76 mm
Max. workpiece dimensions Tens of centimeters Tens of centimeters Tens of centimeters
Drying In air, freeze drying In air, freeze drying None
Debindering No further requirements No further requirements Powder bed, thermal (slow)

REVIEW
colloidal gels facilitated manufacturing of free spanning 3D teric dispersants) in the solvent by agitation with shakers, ball
structures without the need for a fugitive support materi- mills, planetary mills or ultrasonic probes until homogeneity
al.[146] FDC was first mentioned in 1995. In this first is achieved.[135,144,146,150] Then a polymeric viscosifier/binder
publication, a commercial FDM apparatus of Stratasys, Inc. is added to prevent sedimentation and solvent migration, to
(Eden Prairie, MN, USA) designed for polymers was used to ensure consistent extrusion and to provide green strength.
deposit ceramic powder-loaded extrudates.[122] About the After complete dissolution of the viscosifier, the suspension
same time, MJS was developed and first mentioned in can be degassed by vacuum[125] or centrifugation[139,140] and
1994.[141] Commercial services have emerged in the past then filled into the cartridge. If a colloidal gel is to be applied
decade, thus EFF devices (repetition parts) and services are to EFF to offer improved shape retention for extrusion of free
available (e.g., Robocasting Enterprises LLC, USA, Envision- spanning filaments, tubes or special filament geometries, the
Tec, Germany); but among EFF technologies, ceramics are still slurry can be coagulated using several mechanisms (Van-der-
primarily objects of academic research. Waals forces, bridging flocculation and depletion flocculation)
by adding salts, pH-modifiers or polymers.[146,150] Conrad
4.2. Feedstock Preparation and Properties et al.[151] published a detailed description of designing
colloidal suspensions for EFF. The authors report that, due
Feedstocks for extrusion freeforming have the following
to the high solids loading, extrudability is heavily affected by
common requirements:
local fluctuations in solids loading. This drawback can be
1. A high solids loading to counteract shrinkage and cracking avoided by using biphasic suspensions containing attractive
due to sintering or binder burnout. and repulsive particles. Thus, the rheology can be tailored by
2. A homogeneous particle distribution to ensure a constant the ratio between these two species without changing the pH,
flow and to avoid flaws due to agglomerates. coagulant, or solids loading. Furthermore, these feedstocks
3. Entrapped air should be minimized. facilitate the usage of very small orifices.[152]
4. Solvent migration and sedimentation of particles must be Another approach is to embed particles into a thermor-
prevented to ensure constant flow and storage stability.[17] eversible hydrogel.[147,153–155] This route is also applied in so-
5. Suitable rheology for the applied process to ensure shape called bioplotting, which works similar to FDC whereas the
retention and good welding of the filaments. liquid phase of the feedstock is not frozen upon deposition but
6. Suitable particle size and distribution for the applied passes a gel point and thus solidifies in a cooled bath. For UV/
nozzle dimensions. heat-curable inks, the powder is embedded and dispersed into
7. A binder phase that is easy to drain, dry or burn out. a monomer/oligomer liquid doped with UV-sensitive poly-
8. Suitable solidification kinetics (for instance vapor pres- merization initiators. Furthermore, shape retention by cross-
sure, thixotropy, thermal conductivity and capacity, Tg and linking the binder molecules can be achieved by mixing two
melting points). components continuously in a mixing chamber shortly before
9. Suitable interface properties for adhesion and fusion of exiting the nozzle while deposition is carried out (Table 2).[156]
filaments.
4.3. Rheology
In FDC, mostly a dried and surfactant pre-coated powder The most important property of an EFF feedstock is the
(1 mm) is incorporated in the organic binder vehicle at high rheological behavior, which influences shape retention and
temperatures (above Tm) and shear forces consisting of an extrudability. All feedstocks for EFF show a shear thinning
amorphous base binder, a tackifier to add tackiness and behavior during deposition, mostly accompanied by a
flexibility, wax to lower the viscosity and add stiffness, and significant yield stress <1000 Pa. They are viscoelastic and
plasticizer to add flexibility.[148] The process is thus similar to can be described as Herschel-Bulkley fluids.[146,157] Further-
the one applied when manufacturing a feedstock for injection more, these materials are thixotropic,[150] which promotes
molding. When homogeneity is achieved, the feedstock is filament fusion and requires additional considerations
extruded to form a filament which fits into the liquefier of the regarding delayed deposition and handling of extrudates.
FDM machine. Another approach is to generate a pourable Viscosities range from 10 to 100 Pa s in the extrusion process,
granulate by chopping the filament strand. Special attention while the shear elastic modulus ranges between 0.1–1 MPa.
has to be paid to the mechanical properties of the feedstock: Coagulated feedstocks exhibit a fractal-like particle structure
the wire-like extrudate must be wrappable on spools and rigid where particles are not separated but arranged in clusters,
enough to act as a piston for the liquefier (buckling must be which is a limiting circumstance for the minimum applicable
prevented).[149] nozzle diameters.[158]
Most preparation routes for RC and FEF feedstocks follow Regarding FDC, temperature has a pronounced influence
the same principle. The first step to obtain a feedstock is an on rheology. The temperature must be optimized in order to
aqueous or non-aqueous homogeneous slurry of powder promote welding of the filaments, which is also influenced by
particles having a high solids loading (mostly >50 vol%). heat capacity and thickness of the filaments, thus filaments
Therefore, particles are dispersed (mostly aided by electros- thinner than 100 mm are difficult to handle.[123] FDC

REVIEW
Table 2. Feedstock ingredients for the several EFF techniques.[123,124,133,142,144,146,148,150]
Freeze-extrusion
Technique Robocasting fabrication Fused deposition of ceramics
2 1
Particle properties 30 nm to 2.2 mm, max. 15 m g Similar to RC 1 mm
Volume fraction particles [%] <61 50 <55
Solvent Water/LMW organic solvents Water –
(water, 2-propanol)
Dispersant Polyelectrolytes (mostly PAA), Polyelectrolytes Oleates (steric), oleyl-alcohol,
steric dispersants stearic acid
Binder/viscosifier Cellulose derivatives, PVB Polyoxazoline High molecular weight amorphous
polyolefin, ethylvinylacetate
Other additives Coagulant (polyelectrolyte/salt, pH modifiers); Glycerol (water prevents ice LMW partly crystalline wax,
defoamer (octanol); crosslinkers formation during extrusion) hydrocarbon resin (tackifier),
elastomer, low molecular
weight polyolefin (plasticizer)
feedstocks show Arrhenius-type temperature depen- parameters resulted in structural parts almost reaching the
dence.[157] In RC, the flow profile in the extrusion nozzle properties (strength, density) of conventionally produced
proceeds in a three zone profile: According to Smay et al.,[146] a ceramics. For RC using colloidal gels, the shape evolution of
slip layer forms adjacent to the nozzle wall on which the spanning filaments was described statically[146] and time
filament glides. Thus, the filament itself is hardly sheared. A dependent.[139,162] Cesarano et al.[163] modeled drying behavior
yielded zone forms next to the slip layer, which promotes in RC using dilatancy for shape retention. Gomes de Sousa
filament fusion. At lower shear stresses present in the middle et al.[164] reported the influence of surface tension on shape
of the filament, a solid core is assumed to exist, which is evolution for low yield-stress fluids. Schlordt et al.[140] made
beneficial for shape retention. suggestions for the stability of self-supporting tubular fila-
ments. The ABEF process was analyzed and successfully
4.4. Devices for Robotic Deposition controlled in order to attenuate detrimental effects of air bubbles
and agglomerates.[124] Regarding FDC, the times needed for
For the application of EFF, one utilizes either a moving
solidification were approximated to elucidate issues regarding
substrate or a moving dispenser. Dispensers for gels or slurries
poor welding of filaments at low filament diameters.[123]
may be ram extruders, progressive cavity pumps or air-pressure
Venkataraman et al.[165] calculated and tested conditions to
operated cartridges, while primarily a filament fed extruder
avoid feedstock-filament buckling issues in FDM.
(liquefier) is used (granular media was also applied) among
FDC.[138,141] Extruders may be pressure controlled or volume
controlled, whereas pressure control requires calibration of the 4.6. Drying, Binder Burnout, and Sintering
volume flow, which is highly sensitive to the rheological
Thanks to the high content of volatile solvent among EFF,
properties of the feedstock. The easiest way to establish FDC
time-consuming process routes can be avoided.[133] Deposit-
was to use a commercial Stratasys machine for polymer-based
ed parts either dry partially during fabrication to maintain
RP, thus only the feedstock had to be loaded with ceramic
their shape or the drying process is decoupled from
particles. For the high deposition velocities,[139] a moving
deposition using an oil bath and subsequent drying.[146]
extruder (attached to a robotic arm/gantry) with a rigid
To avoid inhomogeneous drying and warping (frequently
substrate was utilized, which prevents shaking of the already
while drying in air), the specimen can be frozen and freeze-
built workpiece and also is beneficial for big structures with a
dried.[140] Thus, no drying shrinkage occurs and porosity is
high mass. Thus, deposition velocities of up to 150 mm s 1 can
maintained throughout sintering. The advantage here is that
be achieved,[130] which may be detrimental for accuracy due to
freezing conditions can be used to influence the pore
the inertia of the extruder. Deposition devices proved to deposit
structure (“ice templating”).[166] After drying, binder,
more than one material in one workpiece either by mixing
dispersant, and other small amounts of additives are left.
pastes or by alternating deposition and thus achieved graded
Due to their low content, they can be burned out within the
structures.[145,156,159,160]
sintering process and high heating rates can be achieved.
FDC green parts with a high polymer content require special
4.5. Process Modeling and Control
attention while debindering. This can either proceed solely
Several authors have described processes in detail, thus only thermally or be aided by capillary forces to drain the
an overview can be given in this review. Generally, EFF exhibits liquefied binder into a powder bed.[137] Remaining open
specific defects arising through the use of filaments, which pores support further thermal decomposition of the binder.
Agarwala et al.[137] described in detail. In this and other During sintering, EFF workpieces experience anisotropic
publications regarding FDC,[161] the optimization of processing shrinkage.[127,154,161]

REVIEW
4.7. Present and Future Applications textures can develop from non-spherical particles; this
phenomenon can be used to achieve templated grain growth
A commercial use of EFF of ceramics is hardly established.
if a crystallographic orientation of the ceramics phase is
Customized products can be ordered on a small scale. They
desired.[161] Graded structures composed of three materials
include filters, laboratory equipment, catalysts, and catalyst
designed for aerospace applications have been built with FEF;
carriers (Robocasting Enterprises LLC). Extrusion freeformed
they exhibit the biggest dimensions among EFF items (more
parts may find usage as solid ceramic prototypes,[137]
than 10 cm in height).[160] Most recently, RC feedstock recipes
photonic bandgap structures,[119,167–169] piezoactuators,[145]
were improved by using a single additive (carboxymethyl-
microbatteries,[170] graded structures,[160] biomateri-
[125,144,147,154,155,164,171–182] cellulose) as a dispersant and rheology additive.[177,178]
als, as well as military and aerospace
Figures 5–7 show ceramic parts generated by EFF methods.
applications, such as radomes and missile propulsion
nozzles.[160]
5. Stereolithography (SLA)
4.8. Novel Developments
The word “Stereolithography” is derived from the terms
Many researchers are currently working in the field of “stereo,” describing a three-dimensional process, and “lithog-
biomaterials and electromagnetic bandgap struc- raphy,” meaning the print of elevated or recessed structures
tures.[119,167,168] Hard tissue scaffolds have been a subject of onto a plane surface. Starting from a complex CAD model, a
extensive research, especially among robocasting, as porosity solid structure is built up layer by layer from a photo-
and elastic properties can be easily and precisely tailored and sensitized monomer resin or solution containing a photo-
extrusion fabricated scaffolds offer good strength at high sensitized monomer. In the process, certain areas on the
porosity and match the elastic properties of human bone surface of the photocuring liquid are converted into solid
well.[155,172] Regarding biomaterials, RC was also used to parts through exposure to light of certain wavelengths.
create dental prostheses.[183] Furthermore, various nozzle Monomers at the irradiated areas are polymerizing upon their
geometries have been tested, making it possible to retain cross exposure to light. Single layers of polymer are created and
sections having circular, quadratic, hexagonal and annular stacked onto each other in this fashion. The finished polymer
shapes. Gomes de Sousa et al. applied coextrusion of HA filled layers are drawn away from the point of incidence of the light
with a fugitive support material to obtain annular filament beam by a movable stage, and are thus immersed into the
shapes, whereas Schlordt et al. fabricated self-supporting photocuring liquid after their generation. Once immersed into
tubular structures.[140] It was also shown that generation of the liquid, uncured liquid covers up the polymer layer. If the
high porosity on multiple scales was possible by adding surface of the photocuring liquid is open to the outside (free-
PMMA microbeads to the feedstock. Inks for EFF can surface method), the photocuring liquid has to be smoothened
additionally contain a UV curable resin, which renders 2D by a wiper blade before starting the following layer.
and 3D lattices flexible, thus wrapped and folded structures In stereolithography, the finished structure obtained has to
can be manufactured and post-processed by cutting, joining be post-cured after it is built up. This is done either through
and punching. This flexibility can also be achieved by heat-treating or irradiation of the entire surface with UV light.
enhancing the time frame of drying by using a special In this way, any remaining monomers within the structure are
feedstock recipe.[184] The UV-curing aided approach[135,136] polymerized. Ceramic stereolithography (CSL) is an extended
was enhanced, thus layerwise deposition with intermediate method of stereolithography in which the obtained structures
curing steps is no longer needed, which facilitated the are converted into ceramic parts. The process of CSL can be
formation of robocast microscale springs “on the fly.”[185] subdivided into direct or indirect CSL. In the direct CSL
Among FDC, a screw extruder instead of a continuous process, a photocuring liquid filled with a high amount of
filament was used as feedstock, which is fed with a granulated ceramic fillers is cured and the resulting green body is heat-
feedstock.[138] As known from other extrusion processes, treated to generate the green body for the desired ceramic
Fig. 7. Typical alumina lattice truss structure created by robocasting.[139]

REVIEW
Fig. 8. From left to right: different CSL structures that can be employed as molds for turbine airfoils (fused silica), [217] as microwave-guides (zirconia), [196] and as bone implants
(hydroxyapatite).[205]
structure. By contrast, in the indirect CSL process, a non-filled curing liquid. A simple approximation for the line width of
photocuring liquid is cured and then used as a mold for the cure track, Lw, can be calculated by Equation 2, under the
ceramic casting. Due to an adjacent heat treatment, the assumption of a Gaussian profile for the intensity profile of the
ceramic particles in the green body or the ceramic casting are incident light:[214,223–225]
consolidated by sintering. CSL has grown in importance since
sffiffiffiffiffi
ffiffiffiffiffiffiffiffiffiffiffiffiffi
ffiffiffi
its first development in the 1990s. Nowadays, CSL is used in pffiffi Emax
medicine for dental and bone healing applications, in LW ¼ 2 W0 ln ð2Þ
Ec
microtechnology for the production of microelectro-
mechanical systems (MEMS), sensors, piezoelements and where W0 is the Gaussian half width of the light beam. This
photonic crystals, and also in large scaled applications such as approximation applies well to the case of a pure photocuring
turbine blades or mechanically durable structures.[195–222,295] monomer being irradiated by a laser beam. The monomers in
Figures 8 and 9 show ceramic structures generated by CSL the main component of photocuring liquids are either
and used for several different applications. monomer resins, such as derivatives of vinyl ether, acrylate,
epoxy, and oxytane, or aqueous solutions with monomers,
5.1. General Principle such as acrylamide derivatives.[226] In both cases, the photo-
In a single, selective exposure to light, a solid cure track is curing liquid contains small concentrations below 10 wt% of a
created in the photocuring liquid resembling the shape of a photoinitiator that triggers the photopolymerization reaction.
rounded cone, oriented with its tip away from the flat surface During curing, the monomers undergo a radical photo-
of the former liquid. The profile of a cure track is determined polymerization, or alternatively, undergo an ionic photo-
by a certain line width and by a certain cure depth, Cd, that can polymerization.[213,227] Thus, the disadvantage of radical
be calculated using the Jacobs equation: polymerization lies in its sensitivity towards the diffusion
of oxygen from the air into the photocuring liquid. Whereas,

Emax unlike radical photopolymerization, ionic photopolymeriza-
Cd ¼ DP ln ð1Þ
Ec tion does not stop immediately after the end of the light
exposure.[223] Heat is generated during both of the photo-
where DP is the penetration depth of light, Emax (in J m 2) is polymerization reactions, which can lead to a curl distortion
the peak value for the light exposure deduced by the of the photocured structure or to an increase in shrinkage
Lambert–Beer law and Ec is the minimum critical exposure when sintering the photocured structure. Construction errors
to light needed to initiate to polymerization of the photo- in the finished structure can be prevented by considering the
Fig. 9. Alumina drill bits (left) and mesoporous tricalcium phosphate structures (right) at above 99.5% of theoretical density manufactured using CSL (published courtesy of
Homa & Co. KG, Vienna, Austria).

REVIEW
light energy released for one single exposure and the evoked sions with ceramic particles in the submicron and nanometer
heat of reaction in a mathematical model. Corcione et al.[228] scale can be used for this purpose. However, lowering the
proved that the temperature rise within the photosensitized particle size causes increased light scattering within the
liquid is proportional to the applied energy dose during an photocuring liquid. Different photocuring liquids with
exposure, the distance from the center of the light beam, as acrylate derivatives and 10–40 vol% of alumina particles of
well as the inverse of the scanning speed. 0.5, 1.4, and 2.3 mm in size have been tested.[233] To avoid
Photocuring liquids react differently to light exposure increased light scattering, a photocuring dispersion with
when ceramic particles are introduced in the liquid. The nanoparticles and silica glass spheres of 40–80 nm was mixed
ceramic particles are chemically inert and block off the with acrylate derivatives. For instance, a photocuring liquid
incoming light from the monomers by scattering. Therefore, a with 20 vol% of the silica glass spheres transmitted above 70%
more accurate description of the curing process can be of light at wavelengths of 300–400 nm.[213] Organosilicon
achieved by involving the Kubelka–Munk model in theoreti- compounds have also been employed in the photocuring
cal calculation. Originally developed for describing the light liquid. A cubic SiCN structure with sides of 5 mm in length
scattering within layers of turbid substances such as paint, the and submicrometer-sized quadratic pore channels was
Kubelka–Munk model takes the changes in reflectance, fabricated by means of stereolithography on a silizane
transmittance and absorbance into account that arise when derivative and an adjacent heat treatment at 600 °C under
ceramic particles are added to the photocuring liquid. The nitrogen atmosphere.[232] Alumina structures produced by
value of the radiation energy released at a certain depth, z, direct CSL from a photocuring liquid with a solid loading of
inside the photocurable suspension with ceramic particles is 53 vol%, had a density of 90.5% of theoretical density.[224]
given by the following relation:[229] Ceramic structures with a density of 62.45 vol% and a layer
h pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi i thickness of 200 mm were obtained by applying aqueous
E ¼ Emax exp KðK þ 2 SÞ z ð3Þ ceramic dispersions with at least 50 wt% of silica particles of
an average size of 1–10 mm.[231]
Along with the density of ceramic structures from CSL, the
where the specific scattering coefficient, S, and the specific
mechanical strength of ceramic structures from CSL is also of
absorption coefficient, K, depend on the total reflectance of a
importance. One important example for this in medical
layer, on the optical thickness of a layer and on the physical
applications is the compressive strength of HA implants,
density of a layer. When applying the Kubelka–Munk model,
which can replace missing bone tissue and support renewed
the penetration depth, Dp, becomes proportional to the term
bone growth. Although such implants have to contain a
1/S. Thus, the reflectance term can be substituted by the
certain pore structure, at a porosity of 35–75%, in order to
reflective indices of the photocuring liquid, n0, and of the
enable the penetration of osteoblastic cells, the implants can
ceramic particles, np. Moreover, the density of the optical
reach a compressive strength value of 30 MPa, which is
medium can be included by the average size of the ceramic
comparable to coralline HA material.[198] A more recently
particles, d50, the wavelength of incoming light, l, and the
produced implant for the interface of the bone and the
interparticle spacing, F:[216,229–231]
cartilage tissue, consisting of a porous ceramic beta-TCP
structure with enclosed collagen, displays a compressive
2 d50 l n0
DP / ð4Þ strength of 12 MPa. This kind of implant offers the
3 f Dn2
advantage of being able to be fully absorbed by the patient’s
body during the regeneration of injured tissue.[195] In another
where the difference between the reflective indices of the medical application, the flexural strength of dental crowns
particles and the medium is given by Dn ¼ np n0. In a more made of alumina was raised from 105 to 415 MPa by
recent study, Gentry and Halloran investigated the contribu- multiple infiltrations with La2O3–B2O3–Al2O3–SiO2 dental
tion of ceramic particles to the profile of the cure tracks of glass at a temperature of 1100 °C for two hours after sintering
photosensitized liquids. Due to the light scattering of the the ceramic structure from the photocured green body.[203] In
particles, the cone-shaped profile of the cure tracks is addition to bioceramics, a solvent-based photocuring liquid
broadened, while the penetration depth is decreased. Thus, with alumina particles was applied in CSL and the photo-
the penetration width (or width sensitivity) and the critical cured structure was sintered at 1600 °C, which led to dense
exposure in the lateral direction can additionally be consid- ceramic structures with flexural strengths of up to 476 MPa
ered allowing a more precise calculation of the cure track and density values of 98% of theoretical density.[232] In
profile.[225,232] comparison to that, ceramic structures of zirconia stabilized
After finishing a CSL process, the sintering during heat alumina with a flexural strength of 175 MPa were manufac-
treatment determines the theoretical density of the desired tured by photocuring a dispersion of an acryl zirconate
ceramic structure. By increasing the crosslinking density of derivative and 50 wt% of 1.8 mm-sized alumina particles,
the photocured polymer of the green body, the density of the when sintered at 1600 °C.[200] Furthermore, reaction-bonded
sintered ceramic can be increased while reducing the silicon carbide with a flexural strength of 128 MPa was
shrinkage due to heat treatment. Stereolithography disper- produced by the post-infiltration of a carbon structure, which

REVIEW
had been formed by the CSL process and had a porosity of more than 10°.[211] This process is referred to as projection
27%, with molten silicon.[220] microstereolithography (PmSL) and has been demonstrated to
generate micrometer-sized scaffolds with wall thicknesses
below 150 mm for biomedical and engineering applica-
5.2. Process Extensions
tions.[197,199] Although PmSL has not been applied for
In most recent works in the field of CSL, the photocured photocurable ceramic dispersions yet, the incorporation of
green bodies were formed by UV lasers such as helium this method is conceivable for future applications of CSL.
cadmium gas lasers, argon ion lasers, or solid-state
lasers.[3,214,216,230,234–236] However, Griffith and Halloran[230] 5.3. Prospects and Challenges
demonstrated that the lasers can be replaced by LEDs or
The requirements imposed on the finished ceramic
halogen lamps when applying a mask to transfer a desired
structure after photocuring and heat treatment are its
pattern on the photocuring liquid. The method of micro-
mechanical stability, smooth surfaces and a reliable match
stereolithography (mSL), originally developed by the research
with its original CAD model. Therefore, multiple cured tracks
group of Maruo and Ikuta, requires the addition of an optical
have to be overlapped with each other in order to generate a
lens, such as a microscopic lens, to focus blue laser light with a
uniform connection between the numerous curing tracks. The
wave length of 442 nm to the CSL process. For the precision of
lateral overlapping is referred to as linewidth compensation,
mSL, it is necessary to irradiate the photocuring liquid by short
while the vertical overlapping determines the layer thickness
light pulses, in synchronization with the scanning speed. By
of the cured structure. However, the cure track profile imposes
doing so, the photocuring activity (or quantum yield) of the
multiple challenges to the part design in stereolithography
photocuring liquid is decreased in comparison to the photo-
processes. One prominent example of an effect causing
curing activity at UV irradiation, but at the same time it is
roughness on inclined surfaces is the ladder effect, as depicted
possible to selectively cure small amounts of monomers at a
in Figure 10.[239]
certain depth below the liquid surface. Micro-ring rotators on
Facing these challenges in stereolithography, the recom-
shafts of less than 10 mm in diameter have been constructed
mendations for the part design are to avoid the incorporation
through the application of a He–Cd laser with a wavelength of
of small-sized round features within a single production step,
442 nm and a urethane acrylate derivative as the photocuring
as well as the curing of layers with different thicknesses, while
liquid. Here, the light exposure per pulse amounted to
building profiles perpendicular to the cured layers in order to
2.16 mW mm 2 at a scanning speed of 2.5 mm s 1, while the
compensate errors due to the flow of yet uncured liquid.[219] In
lateral and depth resolution for the cured structure were both
the case of CSL, the linewidth compensation is the most
0.43 mm.[237] This mSL method can be transferred to the
significant design parameter and is responsible for increasing
manufacture of ceramic structures (mCSL). Ceramic micro-
the lateral shrinkage of generated ceramic structures.
gears with a diameter of 1027 mm and a thickness of 400 mm
However, freeze-drying the green body before heat treatment
have been presented in the work of Zhang et al.[216] mCSL has
proved to lower the lateral shrinkage of ceramic structures
also been tested for manufacturing photonic crystals for
significantly.[225,238] The occurrence of cracks due to uncured
millimeter wave components, useful as microwave absorbers
or microwave guides. The research group of Chartier et al. has
designed millimeter wave components made of alumina and
zirconia that can reflect microwaves at frequencies of 121 and
145 GHz, causing the strength of signals with these frequen-
cies to decrease by 35 dB.[238] In comparison, microwave
guides constructed by CSL have reflected radiation at
frequencies in the range of 10–12 GHz, causing the signal
strength to decrease by 40 dB.[235] An alternative approach
towards mCSL allows the production of micrometer structures
on the surface of ceramic parts. In this way, a regularly shaped
surface profile with a roughness in the range of 10–200 nm can
be achieved by manufacturing millimeter-sized molds and
using them for ceramic dispersions with micrometer-sized
particles.[215]
Alternatively, polymerizing the photocuring liquid by
means of a pulsed laser light source (a UV light source can also
be used) focused by a digital micromirror device (DMD) or
“dynamic mask” is possible, as shown by the group of Sun
et al. Here, the dynamic mask consists of an array of mirrors of
Fig. 10. A schematic drawing of the ladder effect on a cured structure with inclined
up to 30 mm in size, which can project a single light beam with surfaces (with the outlines of single cure tracks indicated as rounded cones and the
a spatial resolution of 1.1 mm by tilting the mirrors at angles of theoretical surface marked as dashed lines).

REVIEW
photocuring liquid can be caused by an intensified shrinking layerwise before lamination and it does not work as a support
at thermal debinding, relative to the rest of the green body material. A technique called laminated tape (LT) is commonly
structure.[213,240] applied in electronic ceramics technology, especially for the
Besides the structure design and the machine parameters in use of ceramic green tapes.[248] Several review papers have
CSL, the composition and the rheological properties of the described the versatile types of solid freeform fabrication
photocuring liquid can also be varied. In order to achieve an techniques,[249–251] while others have focused on the advan-
optimal interconnection between the cured layers and smooth tages and possible applications of the LOM process.[252] The
surfaces of the cured structure, a viscosity of the photocuring low temperature lamination process prevents distortion and
liquid in the range of 10–5000 mPas has proved to be deformation due to low thermal stresses. The material,
beneficial. A photocuring liquid of low viscosity helps to wet machine, and process costs are low compared to other SFF
the surface of a newly formed polymer layer with less surface techniques. In relation to part sizes up to a volume of
distortions and is easier to be removed from a finished, cured 500 800 500 mm3, accuracy over work envelope is
structure than a highly viscous photocuring liquid would 0.25 mm.[250,252] Hollows can also be produced using the
be.[223,240,241] Dispersions that contained up to 58 vol% of CAMLEM method.[247] A disadvantage is the decubing of the
alumina particles of an average size of 0.5 mm, together with parts, which prevents the creation of very detailed surfaces. In
an amount of 0.6 wt% of a dispersant, have been tested post-processing the organic binder material has to be removed
successfully as the photocurable ceramic dispersions based on between and within the single layers, which results in
acrylate derivatives with the highest amount of fillers.[224] anisotropic mechanical properties.[253–255] To improve the
Studies show that the photocuring activity correlates with the LOM process and/or eliminate disadvantages, research
liquid viscosity, as photocuring itself is dependent on focused on the lamination and cutting process as well as on
diffusion processes. For this reasons, the dynamic viscosity the waste removal strategy. The influence of the roller speed,
of the photocuring liquids is also of interest. Dispersions of size, and temperature on interfacial stresses and lamination
photosensitized acrylate and silica particles with an average was calculated. Bigger rollers are lead to better lamination of
particle size of d50 ¼ 2.25 mm display a shear thinning behavior the sheets, while small rollers enable shorter process times
when the silica content is below 20 vol%, but a shear due to concentrated stress distribution at the interface.[256] The
thickening behavior for higher filler loadings.[217] Shear temperature development during the lamination process of
thickening is also reported to occur in photocuring ceramic curved parts using a heating plate was investigated by placing
dispersions containing HA particles with particle sizes in the thermocouples between the layers. Resulting data were
range of 30–60 nm. In these dispersions the ceramic particles confirmed by a mathematical model based on one-dimen-
agglomerated after a duration of 10 s.[201] However, shear sional transient heat conduction.[257] The separation of the
thickening can be successfully suppressed by including a heating and pressing (rolling) process leads to a shorter
comb-polyelectrolyte in the stereolithography dispersion, manufacturing time, since the heat affected zone is bigger in
acting simultaneously as a surfactant and as a dispersant. the xy-direction than for the heating while rolling where the
This procedure has already been applied for colloidal heating zone is extended in z-direction. Applying heating
dispersions with different contents of nanometer-scaled temperatures up to 450 °C before pressing allows increased
alumina particles and zinc oxide particles in photosensitized moving speed.[258] Before shaping, the laser energy has to be
acrylate.[240] The potential of low viscosity photocurable adapted to the material system and layer thickness. An
dispersions with acrylate derivatives and nanometer-sized analysis of variance for the influence of the cutting speed, the
particles of alumina, titania, a-Fe2O3, as well as Fe- laser power and cut profundity led to a maximum tape
(C2O4) H2O as ceramic fillers, was demonstrated by de thickness.[259] A lot of work has also been invested in the
Hazan et al., who have produced ceramic fibers of a diameter optimization of the decubing process. Normally, waste
below 10 mm, as well as ceramics with a regular cell structure material volume is cubed for easier removing. Dividing the
and a porosity of 80%.[242] The viscosity of aqueous waste volume into two sections of coarse cubes in the outer
dispersions of acrylamide derivatives and 50 vol% of silica sections and fine cubes in the inner region saves laser energy,
particles, employed in CSL, have even undercut the viscosity protects the part, improves the machining efficiency, and
value of 1000 mPa s.[246] shortens the decubing time.[260] Additionally, decubing time
can be reduced by planning the laser path of the burnout
rule on sloped surfaces. Laser energy has to result in the
6. Laminated Object Manufacturing (LOM)
decomposition of the adhesive in the working zone up to a
In 1986, the Helisys Corporation developed the laminated critical inclination angle, where the overlap zone between the
object manufacturing process for creating three-dimensional cuts of two layers becomes too large. If horizontal or areas
parts from sheets of paper, plastic or metal. The process was with inclination below a critical angle are avoided, decubing
patented in 1987 and the first LOM machine (LOM-1015) was time can be significantly reduced and surface quality
commercialized in 1991. Other research groups have called it improved.[261] If the waste material is removed during the
computer-aided manufacturing of laminated engineering process, hollow shapes can also be produced. A self-adhesive
materials (CAMLEM).[247] In CAMLEM, waste is removed sheet material with a shielding paper is required to remove

REVIEW
waste material, with the adhesive on the top of the sheets. green sheet tensile strength of single layers and laminates was
Areas that have to be removed are printed with graphitic investigated and applicability for the LOM process was
powder on the layer below to prohibit fixing. Waste parts are proved.[272] The LOM cutting parameters (cutting speed and
also removed by removing the shielding layer.[262] Bridging laser power) were adjusted to the LZSA system and maximum
elements can be inserted to create freestanding parts, which cut profundity of 220 mm was determined.[259] Their sintering
have to be removed after decubing.[263] The resulting parts behavior was characterized before and after binder burnout
normally offer a stepwise surface roughness. It was discov- (750 °C) and sintering (850 °C), which led to a new phase
ered that the nature of surface roughness is affected by the formation of b-spodumene and lithium metasilicate. By
paper thickness and the orientation angle, and can be changing the stack orientation for 90°, an increase of bending
controlled by the working distance.[264] Investigations using strength from 70 to 120 MPa was achieved.[273] The
a statistical analysis show a great influence of heater addition of ZrSiO4 affected an almost constant thermal
temperature, layer thickness and laser speed on the surface expansion coefficient up to 600 °C.[274] Porosity values
roughness in z-direction.[265] Accuracy in xy-direction in >10% at the lamination interfaces prohibit bending strength
dependency of machine parameters and in correlation to >130 MPa.[274]
build-time have been investigated.[266,267] A model has been Other material systems like glass-fiber reinforced poly-
proposed for calculation and optimization of surface rough- mers, SiC, SiC-fiber-SiC, AlN, Si3N4, HA, and TiC/Ni were
ness for varying part orientation.[268] used. For SiC samples, a tape casting slurry containing a
Generally, the LOM technique was developed for process- bimodal SiC mixture, carbon black and graphitic powder was
ing paper. In transferring it to ceramic processing, research mixed with a polymeric binder. The LOMed parts of these
has focused on using ceramic tapes as building materials. tapes were pressed in a powder bed to affect densification in
LOM of ceramics started with Al2O3 tapes, which exhibited the z-direction. After pyrolysis of the binder, the SiC/C
mechanical properties comparable to pressed samples. composite was infiltrated with Si to build secondary SiC.
Bending strength was also discovered to be isotropic, parallel Mechanical properties were decreased in comparison to
and perpendicular to lamination orientation.[248] Bending commercial SiSiC due to residual Si layers at the interfaces.
strength of LOMed alumina samples was improved by Curved body armor parts were produced from the SiC tapes,
creating an alternating composite structure of Al2O3 and Ce– but large overlap areas led to complications while removing
ZrO2 layers from 311 MPa for Al2O3 up to 688 MPa for the waste material.[275] A curved layered LOM process was
alternating composite.[253] Since more complicated parts with developed to minimize overlap areas.[276,277] The tapes were
angular surfaces or hollow structures were to be produced, placed on a mandrel with the desired curvature and
the CAMLEM was applied. The single sheets were cut and the laminated by a flexible thermoforming mechanism, Figure 11.
waste material was removed before stacking and lamination. The tape-cast SiC sheets and SiC fiber preforms, infiltrated
The staircase effect was avoided by inclining the laser during with a phenolic resin, were pressed to a two-layer sheet. The
cutting. In this way, alumina parts with internal channel LOMed parts of these sheets were pyrolyzed under pressure
structures were produced.[247] Internal structures for elec- up to 325 °C to avoid delamination and at 700 °C in Ar for
tronic devices have also been prepared with low-temperature complete pyrolysis.[277] Complete densification was achieved
co-fired ceramics (LTCC) containing a SiO2–Al2O3–RO glass
and Al2O3 particles. In contrast to the Helysis device, these
tapes were cut using a milling plotter (LPKF Laser &
Electronics, Garbsen, Germany) and cold laminated with a
double-sided adhesive tape with a thickness of 12 mm. Binder
decomposition was finished at 425 °C and sintering at 870 °C
led to a density of 99%.[269] A basic simulation of binder
removal was done for LOMed Al2O3 laminates.[270] The
advantages of this method are the slight lamination pressure
at room temperature, which enables internal structures, and
the milling step which allows preparation of curved
surfaces.[269] Since all Al2O3 sheets for LOM were prepared
using organic solvents, a water-based tape-casting process
was provided due to ecological reasons. The tapes, consisting
of Al2O3 powder, a styrene-acrylic latex binder, water and
some additives, showed good ability for LOM processing due
to their high green strength, which facilitates the coiling of the
tape, and their lamination behavior.[271] Later on, water based
LiO2–ZrO2–SiO2–Al2O3 (LZSA) tapes were laminated using
Fig. 11. Curved layer, monolithic body armor panel, immediately after LOM
the LOM technique. Investigations of the rheology led to a processing. The piece has been fully decubed and placed back on the LOM paper
maximum filler particle content of 27 vol% (72 wt%). The mandrel for illustration. Notice the smooth surface and lack of stair steps.[276]

REVIEW
by a silicon infiltration step at 1600 °C. Resulting dense

samples did not show fiber pullout in mechanical testing.[275]
Epoxy resin and PE-based composites with a glassy fiber
content up to 55 vol% were successfully produced using
LOM.[275,278]
Si3N4 parts with a density of 97% were also prepared with
tape-cast sheets containing Si3N4 and Y2O3 and Al2O3 as
sintering aids.[279] After sintering at 1750 °C, most a-Si3N4 was
converted to b-Si3N4. The resulting bending strength of
918 MPa and fracture toughness of 7.5 MPa m0.5 were in
agreement with conventional data.[279] The LOM process was
also implemented for medical applications. From HA, CP
glass and additives, bioceramic bone implants were produced
using the LOM technique. After pressing at 120 °C and
sintering at 1050 °C, the glassy phase led to a linear shrinkage
of 5%. Flexural strength of 19 MPa was achieved (bone 50–
100 MPa).[280,281] The LOM technique was also used to
produce functional prototypes for telescoping actuators made
from PZT ceramics. Combining the finite element method and
LOM enabled fast and variable prototype manufacturing.[282]
Commercially available green ceramic tapes with a thickness
of 0.2–0.25 mm were laminated with a lamination assisting
solvent mixed with polyvinylbutyral. After binder burnout at Fig. 12. Top view of laser cut LOM-processed Si–SiC gear wheel manufactured from
840 °C and firing up to 1245 °C, the samples exhibit bending SiC-filled preceramic paper and representative SEM image showing the polished
cross section of the fabricated Si-SiC composite (dark phase is SiC, bright phase
strength values up to 109 MPa.[283] is Si).[254]
The conventional way to produce LOM parts is to use
paper sheets. If they are filled with ceramic particles, the 3D
parts can be converted to ceramic structures. Firstly, factured from SiC-filled preceramic paper and representative
commercially available ceramic papers filled with Al2O3 SEM images showing the microstructure of the fabricated
and SiO2 were used and laminated by means of sodium composite.
silicate.[278] Then, the paper derived route was focused on the Different ceramic filled papers (e.g., Al2O3, SiC) and their
fabrication of SiC structures. Pyrolyzed filter papers were interaction with the LOM cutting laser have been discussed as
coated with a polymeric slurry for lamination. After well as their anisotropic sintering behavior due to the
manufacturing in a LOM device with blade cutting (Kira cellulose fiber morphology.[255] Combining the preceramic
PLT A4, Kira Corporation, Japan), the parts were pyrolyzed paper technology and the fiber paper technology offers a high
again and the carbon preform was Si-infiltrated at 1500 °C. potential for novel lightweight structures prepared using the
Resulting bending strength of 130 MPa was comparable to LOM technique. Papers with a thickness of 300 mm were
values measured for LOMed samples derived from tape-cast prepared with Al2O3 particles and fibers.[286]
sheets.[284] Then experiments were conducted dealing with Besides tape casting and paper LOM, Al2O3 and SiC parts
carbon fiber papers, which were coated with a polyvinylal- were also produced from extruded tapes. This time, Al2O3 and
cohol resin. After LOM cutting, the samples were infiltrated SiC powder were mixed with LDPE grains at a weight ratio of
with a phenolic resin. Pyrolyzed and Si-infiltrated samples 75:25 and extruded to rods, which were roll-formed to
exhibited a residual carbon content of 41 vol%, 32 sol% of SiC sheets.[287] In following experiments, Al2O3 was also roll-
and 27 vol% Si, respectively. Bending strength of 160 MPa formed with a polyvinylbutyral binder. The sheets were
was in the range of LOMed SiSiC parts.[285] A strongly laminated with polyvinyl acetate in the LOM. After binder
increased bending strength up to 315 MPa was obtained by removal at 240 °C, the laminates were sintered at 1580 °C.
using a novel SiC-filler loaded cellulosic paper. The sheets Interfacial structures disappeared after binder removal, and a
contained 76.8 wt% of SiC powder after fabrication by the residual porosity of 2.9% led to a bending strength of
Rapid K€ othen aqueous hand-sheet-forming process and were 228 MPa, while 350 MPa was expected from the conven-
densified by calandering to a mean thickness of 240 mm. The tional production process.[288] Roll-formed TiC/Ni sheets
paper sheets were sprinkled with a thermosetting polymeric containing graphite, Ti-powder, Ni-powder and PVA binder
adhesive, which was laminated during the LOM process at were LOMed to a gradient structure with a varying Ti/Ni
140 °C. Adhesive covering resulted in a layer thickness of content. A TiC/Ni composite was generated in a self-
400 mm. After pyrolysis and Si-infiltration, SiC-content up to propagating high-temperature synthesis (SHS). The highest
48.6% was detected.[254] Figure 12 shows top view of laser cut bending strength of 950 MPa was achieved with a Ni content
LOM-processed Si–SiC gear wheel (diameter 50 mm) manu- of 20 wt%.[289]

REVIEW
Laminated object manufacturing offers many opportunities (Premium 4820, i-mes icore, Eiterfeld, Germany). After
for solid freeform fabrication of complex parts with layered pyrolysis up to 1400 °C in N2 atmosphere, a Si–SiC–SiOC–
structures from various ceramic materials. Despite this fact, N microcomposite material was obtained with bending
LOM – like most other conventional RP techniques – has the strength of 250 MPa (see Figure 13).
drawback of very poor surface qualities, especially at round or In comparison to other LOM fabricated materials, the
angular surfaces as the individual layers are cut by laser beams preceramic polymeric tapes are laminated without any kind of
or hauling blades. In contrast, high-speed cutting (HSC) offers adhesive. Figure 13 shows the interlayer of two laminated
the possibility of high-precision manufacturing of complex sheets with varying SiC particle sizes. An additional
parts by milling of complex parts from simple blanks.[269] strengthening effect of the smooth milled surface might be
However, the geometry of the parts is limited by the number of possible by changing the sheet composition. A mixture of
axes the part and the milling cutter can be moved. Moreover, polysiloxane, SiC and FeSiCr, which can be extruded and roll-
undercuts are very hard to produce as systems with five axes or formed to sheets, offers the ability to build a nitridic surface
expensive complex-shaped cutter knives are necessary since the reaction layer, which results in a bending strength increase up
path of the tool can only lead from the edges of the blank to the to 400 MPa. In addition, residual porosity in the bulk material
center and from the top to the bottom. is decreased to 1%.[293]
For the past few years, polymer-derived ceramics have
been shaped by the use of HSC for the production of linear
7. Conclusions
ceramic bearing components.[290,291] Layered ceramic struc-
tures can also be produced from these materials using warm A combination of geometrical design with materials design
pressing without any kind of adhesive. Tapes with different offers the unique possibility to reduce fabrication times and
compositions can be combined to improve the mechanical product costs of the components with required properties
properties.[292] The novel approach of the present work gives when applied properly. Table 3 summarizes the types of
rise to combined laminated object manufacturing and a high- ceramic materials that were processed using AM technologies
speed milling machine, somewhere comparable to Schindler’s and the corresponding processes. However, dimensional
work.[269] The idea is to build a warm press for the production accuracy and surface finish still remain crucial features in
of thermoplastic or duroplastic joinable tapes into a HSC- today’s AM due to the layer-by-layer formation of the parts.
machine where the individual layers are milled from bottom For example, it is complicated to achieve accurate layer
to top layerwise. Therefore, it is possible to mill parts with deposition by spreading fine powder layers during 3D
undercuts without turning the part, and achieve good surface printing or to ensure uniform recoating of a new layer by a
quality in contrast to conventional SFF machines. For the highly viscous ceramic suspension in SLA. Rough surfaces on
present study, sheets containing polysiloxanes, polysilanes, the fabricated parts result from “staircase” effects and are due
SiC, Si, and catalytic substances were tape cast[292] (see to the slicing of a contoured surface. An improvement of
Figure 13). After pre-crosslinking at 120 °C, the tapes were the texture can be obtained by reducing the thickness of the
laminated stepwise in a uniaxial press (B€ urkle, Freudenstadt, single structural elements or by using subsequent secondary
Germany) and milled using a polycrystalline diamond mill operations such as grinding or polishing. However, these
operation steps lead to increased production times and costs.
Unfortunately, every AM process has its own unique
disadvantages in building ceramic or ceramic-metal parts.
For example, SLA exhibits the best part surface finish among
currently available techniques; however, it makes use of very
expensive and a limited range of raw materials (photosensi-
tive resins), while additional care must be taken owing to the
environmentally hazardous solvents used to clean up parts. In
contrast, 3D printing achieves a limited surface finish of the
manufactured parts, yet allows the use of a wide range of
feedstock materials (in principle, any material available in
powder form). Moreover, 3D printing offers the possibility to
control not only the shape of the ceramic parts, but also the
composition, microstructure and properties throughout a
component. Thus, there are still obstacles for these technolo-
gies to overcome before they become “everyday manufactur-
ing methods” in place of “conventional” techniques. In spite
of the fact that significant progress has been made in the
development of metallic and ceramic feedstock materials,
Fig. 13. Layerwise CNC milling (left), ceramic greentape and LOMed part after
pyrolysis at 1400 °C (right) and interlayer between two polymer-derived ceramic the most difficult limitations for AM technologies are the
layers containing FeSiCr and SiC particles (bottom). restrictions set by material selection for each AM method and

REVIEW
Table 3. Ceramic materials and corresponding AM processes.
3DP SLS SLA EFF LOM
Structural ZrO2[28,34,38,39] ZrO2 [90,91,100]

Al2O3[221,224,235,246] ZrB2 [160]
Al2O3[248,278,288]
ceramics Al2O3[21,51,52]
Ti3SiC2[61] Al2O3[91,92,97–99,102] Al2O3–ZrO2[196,238] Al2O3[124,133,139,140,167,187,188] ZrO2[253]
Si3N4[65,84,85] Al2O3–SiO2[94] Al2O3–SiO2[244] Mullite[187,189] SiC/C[285,294]
TiC–TiO2[53,54,86] TiC–Al2O3[96] SiO2[202,213,214,216,217,222,226,241,243] SiC[186] PE-glassy fiber[275,278]
[49,62,63] [95]
SiC SiC TiO2[242,245] Si3N4[190] Si3N4[279]
SiSiC[101] SiC[220]
ZrO2[187] SiO2[278]
Al2O3/SiO2/Mullite/ZrSiO4[199] WC–ZrO2[160] C[284]
ZrC[160] TiC/Ni[289]
Al2O3–ZrO2[191] Polymer-derived ceramics:
see present work
Functional BaTiO3[40,41] PZT[89] PZT[211,223,239] Fe2O3/Fe(C2O4)* BaTiO3[150] SiO2–Al2O3–RO-glass[269]
ceramics 2H2O[242] Bi(VxNb1 x)O4[232]
PZT[37,45–47] BaTiO3[115] SiCN[225] PZT[145,146] LZSA-Glass[272]
TiO2[43,44] PMN[192] PZT[282]
LSMO/YBCO[48] LiFePO4[170]
Li4Ti5O12
BaZrO3, SrTiO3,
BaMn2Al10O19 x[193]
ITO[119]
ZnO[119,187]
La(Mg0.5, Ti0.5)O3[167,188]
Zr0.8Sn0.2TiO4[188]
TiO2[119]
Bioceramics HA[50,66,67,69–72] Apatite-Mullite[107–109] HA[205] Al2O3[133] HA, TCP[280,281]
TCP, TTCP[56,60,73–82] Apatite-Wollastonite[110] HA–Al2O3[204] HA[154,164,171,174,180,182,194]
ZrO2[22,30,36] PEEK-HA[112] TCP[195] TCP[144,147,179,182]
HA-HDPE[113] Porcelain[183]
HA-PA[114] Bioglasses[127,153,155,166,172]
BCP[116] HAP-TCP[154,179]
aspects considering the inner architectural design of the [3] B. Y. Tay, J. R. G. Evans, M. J. Edirisinghe, Int. Mater.
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Final Version: February 27, 2014
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1. Introduction expansion of the use of advanced ceramics in key sectors.[1] It

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

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solely serve as the shape retaining property. Another hybrid

Technique Robocasting Freeze-extrusion fabrication Fused deposition of ceramics

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

Fig. 7. Typical alumina lattice truss structure created by robocasting.[139]

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

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by a silicon infiltration step at 1600 °C. Resulting dense

ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

Table 3. Ceramic materials and corresponding AM processes.

3DP SLS SLA EFF LOM

Structural ZrO2[28,34,38,39] ZrO2 [90,91,100]

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ADVANCED ENGINEERING MATERIALS 2014,

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ADVANCED ENGINEERING MATERIALS 2014,

ADVANCED ENGINEERING MATERIALS 2014,

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