Fabricación de Aditivos para Cerámica Por Fotopolimerización

MR46CH10-Halloran ARI 8 March 2016 14:22
V I E W Review in Advance first posted online

E on March 17, 2016. (Changes may
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still occur before final publication
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online and in print.)
C E
I N
N
A
D V A
Ceramic Stereolithography:
Additive Manufacturing
for Ceramics by
Access provided by Gazi Universities Main Library (D-S) on 03/22/16. For personal use only.
Photopolymerization
Annu. Rev. Mater. Res. 2016.46. Downloaded from www.annualreviews.org
John W. Halloran
Department of Materials Science and Engineering, University of Michigan, Ann Arbor,
Michigan 48109; email: peterjon@umich.edu
Annu. Rev. Mater. Res. 2016. 46:10.110.22 Keywords

The Annual Review of Materials Research is online at photopolymerization, stereolithography
matsci.annualreviews.org
This articles doi: Abstract

10.1146/annurev-matsci-070115-031841
Ceramic stereolithography and related additive manufacturing methods in-
Copyright c 2016 by Annual Reviews. volving photopolymerization of ceramic powder suspensions are reviewed in
All rights reserved
terms of the capabilities of current devices. The practical fundamentals of the
cure depth, cure width, and cure profile are related to the optical properties
of the monomer, ceramic, and photo-active components. Postpolymeriza-
tion steps, including harvesting and cleaning the objects, binder burnout,
and sintering, are discussed and compared with conventional methods. The
prospects for practical manufacturing are discussed.
10.1
Changes may still occur before final publication online and in print
INTRODUCTION
Additive manufacturing (AM) of ceramics can be accomplished with a wide variety of methods,
typically involving a layered manufacturing approach. Three-dimensional objects are produced
by combining many layers, with each layer patterned individually according to the design of the
object. Some of the prominent ceramic AM methods involve photopolymerization of ceramic
suspensions to pattern the layers. There have been several generations of ceramic AM involving
patterning using laser scanning and image projection. This review concerns AM by photopoly-
merization, which is often termed ceramic stereolithography. Stereolithography, strictly defined,
is a process whereby each layer is patterned by laser scanning on photopolymerizable medium
to convert liquid monomer into solid resin (1). The method has been adapted to form ceramics
by using a photopolymerizable suspension of ceramic powders in place of the liquid monomer. I
expand the term stereolithography to include all cases in which ceramics are made with multilayer
photopolymerization, including cases involving layers patterned by laser scanning and by mask
image projection.
Photopolymerization is not a new ceramic process. Photopolymerized tape casting systems

were described in 1986 (2), and photopolymerized dental ceramic composites are commonplace (3).
Photoimageable tape cast products are commercial products (4). The technique was applied for AM
of ceramics using commercial laser scanning stereolithography machines (5, 6) or novel variants
of laser scan devices (7, 8). Patterning can also be done by mask image projection (9, 10), typically
with a spatial light modulator based on a digital mirror device (DMD) (11, 12). Applications are
varied and include biomedical implants (13, 14), ceramic prototypes (15), cellular ceramics (16),
complex investment casting cores (8, 17, 18), and integrally cored investment casting molds (19).
The process has been adapted for microscale ceramic forming as microstereolithography (2022)
for a variety of applications (2325).
Several excellent reviews on AM of ceramics (2629) have been recently published. These
reviews cover the broad range of AM techniques used for ceramics and comprehensively present
the current status of the field. Because the capabilities of various AM methods are available, those
aspects of AM are not repeated in detail here. Instead, this article focuses on methods that involve
photopolymerization of ceramic suspensions. The emphasis is on the practical fundamentals of
the polymerization process as well as on the other steps necessary to produce accurate ceramic
objects by stereolithography.
To provide the reader with some context, below are some early and recent examples of ceramics
built with stereolithography, illustrating the range of designs that can be realized. Figure 1 is an
early example of a ceramic sculpture. It is a digital sculpture by Michael Rees that was built
in alumina (Al2 O3 ) by laser scanning stereolithography by Alan Brady in 1998. This piece is
approximately 5 cm wide and consists of several lobes and appendages. This design could not have
been executed in one piece without using an AM method. Producing it by conventional methods
would have required assembly of separately formed pieces.
Figure 2 shows a lattice structure built from Al2 O3 by Johannes Homa in 2014. The structure
is patterned with a fixed DMD using a Lithoz device. The object is approximately 3 cm tall, with
struts as fine as 500 m. This design could have been built only by AM, as it could not have been
cast or molded.
Figure 3a is an example of an investment casting core, which was built by Brady from Al2 O3
by laser scanning. This object is approximately 6 cm tall. The design of this core is based on a
commercial injection molded core, so although it is a complex shape, it is an object that can be
molded. It illustrates the ability to achieve state-of-the-art features without using injection molding
tools. Compare Figure 3a with Figure 3b, another airfoil core, which was built in refractory silica
10.2 Halloran
a b
Figure 1
Digital sculpture by Michael Rees that was built in Al2 O3 by Alan Brady in 1998 by laser scanning
stereolithography. (a) Top view, approximately 5 cm wide. (b) Detail. Reproduced with permission from the
artist.
Figure 2
Lattice structure in an Al2 O3 -fixed digital mirror device approximately 3 cm tall with 500-m struts. Figure
courtesy of Johannes Homa.
www.annualreviews.org Ceramic Stereolithography 10.3
a b
Figure 3
(a) Investment casting core that was built from a design based on an injection molded core. It was built in
1998 by Brady in Al2 O3 using laser scanning and is approximately 5 cm tall. (b) Investment casting core built
in 2014 by Suman Das in refractory SiO2 using a scrolling digital mirror device. The core illustrates features
typical of a state-of-the-art core, including rods for film-cooling holes in leading-edge serpentines with
turbulence-enhancing surface features and core holes and a flag for the trailing edge.
(SiO2 ) in 2014 by Suman Das using scrolling DMD. This object is approximately 10 cm tall and
has several fine features that could not have been produced with a two-piece mold.
Figure 4 shows a 30-GHz Luneburg lens designed by Brakora & Sarabandi (30) and built
in Al2 O3 by laser scanning by Walter Zimbeck. In this design, focusing is accomplished because
the 30-GHz refractive index gradually changes as the thickness of the Al2 O3 struts varies from
the inside to the outside. This object could not have been fabricated without AM, because the
function of the lens required the Al2 O3 volume fraction (strut size) to vary precisely from center
to exterior.
Figure 5 shows a ceramic box with triple-helix array. This structure was built from SiO2 , with
patterning using a scrolling DMD. The object has 168 intertwined helices, with 56 columns of
three helical rods; each SiO2 rod is 120 m in diameter. This box illustrates both fine features and
the realization of an unmoldable design that was achieved by ceramic stereolithography.
PROCESSING BEFORE PATTERNING

Ceramic AM techniques accomplish only the shaping step, as they are simply forming methods for
the ceramic. They make only the ceramic green shape, i.e., the part before sintering, and not the
finished ceramic object. So such techniques accomplish approximately one-third of the complete
task, with the powder and body formulation done before AM and with sintering, microstructure
development, and finishing done after AM. From the ceramic perspective, ceramic stereolithogra-
phy is just a forming process for a green ceramic. The valuable properties of the ceramic product
10.4 Halloran
Figure 4
A millimeter-wave Luneburg lens built from Al2 O3 . The lens was designed by Karl Brakora and was built by
TA&T with laser scanning stereolithography. The lens is approximately 6 cm in diameter, with Al2 O3 strut
width ranging from 650 m in the center to 340 m at the surface, which varies the refractive index at 30
GHz to focus the millimeter-wave radiation.
depend on the composition and microstructure, which are determined by sintering behavior as
determined by particle size and heat treatment. Stereolithography is thus the same as any binder-
rich ceramic forming technology and is comparable to ceramic injection molding or ceramic tape
multilayer fabrication.
Much of the ceramic technology in stereolithography is similar to conventional ceramic tech-
nology, although it is adapted to work in the stereolithography process. Photopolymerizable
Figure 5
An object built in refractory SiO2 ceramic by a scrolling digital mirror device. This 40-mm box has an array
of 168 intertwined helices, with 56 columns of three helical rods each with 120-m diameter. Figure
courtesy of Michael Middlemass, DDM Systems.
ceramic suspension technology is essentially a type of gel casting (31). As with gel casting (32), the
green density of the formed body is determined by the ceramic volume fraction in the suspension.
For adequate sintering behavior, the green density (and therefore the suspension volume fraction)
must be 50 vol% or higher. So a key feature of the ceramic technology is achieving the proper
rheology of highly loaded suspension (33). Fluid suspensions are used with some stereolithogra-
phy systems (5). Other systems use more viscous pastes (7). The forming behavior is the same,
but there are important differences in the mechanical design of these systems. The key difference
between conventional gel casting and patterning by photo-gel casting is largely the gelation it-
self, which occurs via photopolymerization. Photopolymerization of ceramic suspensions involves
several unique features, as discussed below. The layer-by-layer application method is another key
difference between conventional gel casting and stereolithography. However, the application of
the very thin and uniform liquid layer for stereolithography is similar in some ways to conventional
tape casting.
Further steps are required after all the layers are complete. The nature of these steps depends
on whether the part is self-supported and built from above (see, e.g., Figure 2) or whether it was
immersed in uncured suspension (see, e.g., Figures 1 and 4). There may be temporary support
structures that must be removed (see, e.g., Figure 3a). If the object has trapped volumes (see, e.g.,
Figure 5), the uncured liquid must be drained. If the design has a dense array of small passages
(see, e.g., Figure 4), the small spaces must be cleared of uncured suspension. The object is often
just one part in a multipart build (see, e.g., Figure 3b). Multipart builds are one advantage of
stereolithography, as many different objects can be built during the same run. This approach can
significantly increase productivity, as one run lasting several hours can yield dozens of different
objects, each closely nested to make productive use of the space within the build volume. For
these multipart builds, the individual objects must be liberated from the build volume. Next it is
necessary to remove the uncured suspension from the exterior and interior surfaces. Removing
uncured suspension from the exterior surfaces (see, e.g., Figure 1) or relatively open structures
(see, e.g., Figure 2) involves little cleaning. But removing the uncured suspension from the interior
of complex parts can be a challenge, particularly for parts with tight interior features, such as the
cores in Figure 3, the thin gaps between the struts in Figure 5, or the small spaces between the
helices in Figure 5. After building, the part is a ceramic green body. As with ceramic injection
molding, the space between the ceramic particles becomes nearly saturated in a polymer gel binder.
The binder removal must be done by a well-controlled pyrolysis, followed by high-temperature
sintering. These steps are the same as for conventional ceramic injection molding (34, 35). Binder
removal is easy for designs with thin sections (Figure 2) but is more challenging for designs with
thick sections (Figure 1) or a combination of thick and thin sections (Figure 3b).
The rheological behavior of the photopolymerizable suspension is particularly important for
the deposition of the fresh layers, which are typically only approximately 100 m thick. The fresh
layers must be strictly uniform for high-accuracy builds. It is necessary to control the rheology
over a very wide range of shear conditions. During application of the fresh layer, the shear rate
can dramatically change as the coating device passes from a thick uncured area to a thin liquid
layer on a solid cured area. The fluid dynamics associated with this sudden change in shear rate
is a well-known issue for conventional stereolithography (36). Much of the fresh layer is applied
over the previously cured solid layer, whereas in other regions it is applied over a portion that
has no solid layer, causing perturbations in the fluid suspension. The fresh liquid thickness over a
previously cured solid layer can be 0.1 mm or less, whereas the total liquid thickness where there
is no submerged solid can be 100 mm. As the coating device moves from a deep liquid to a thin
liquid, shear rate and therefore shear stress can change by a factor of 1,000 or more. This change
causes fluid dynamic instabilities in the liquid suspension and can create damaging stresses to
10.6 Halloran
small solid features. The well-known trapped volume problem also presents fluid dynamic issues
that make it difficult to achieve an ideally smooth layer over a complex surface with liquid and
solid regions. Build strategies are incorporated to mitigate the unfavorable fluid dynamic effects
that occur when one is applying and leveling suspension over partially completed layers. The
rheology of the suspension at rest is important for leveling and for preventing sedimentation of
coarse particles. These rheological challenges are addressed by using the principles of colloidal
processing familiar from conventional ceramic forming. Fortunately, for most ceramic powders
suspended in acrylate monomers, the colloidal behavior is often simpler than aqueous suspensions,
and acrylate suspensions can be simple fluids (33, 37).
BUILDING MULTILAYER OBJECTS

As with most AM schemes, the macroscopic object is built from many thin patterned layers. The
typical layer thicknesses range from 25 to 250 m. Thinner layers enable more detail and more
accurate resolution, but at a cost of build time, because each layer takes a certain amount of time
for recoat and for exposure.

For laser scanning stereolithography, the patterning to define the design of each layer (and its
ancillary support structures) is done by controlling the motion of a laser beam, with galvanometer
mirror scanners. The patterning is defined by the instructions that control the scanning of the laser
beam and is similar to drawing with a pencil. The actual polymerized layer is the superposition
of edge contours and interior hatching. The lateral (x, y) resolution is determined by the focal
width of the laser, as broadened by scattering. Laser scanning devices build the object from long,
thin rows, with areas defined by cross-hatching. The hatching style has a second-order influence
on lateral resolution. The typical lateral (x, y) resolution is on the order of 2550 m. Very small
features may appear in the original design files but may be too small to define with the hatching
resolution (46).
Patterning with projected images is quite different. The image is typically projected as a bitmap
of the complete layer or a portion of the layer. The patterning image is projected from a fixed DMD
or a scrolling DMD. The lateral resolution depends upon the projection optics and scales with the
characteristic spatial resolution of DMDs, which usually have 17-m pixels. Fixed DMDs focus
an image with the spatial resolution of DMDs. The fixed DMDs are best suited for relatively small
objects, as they pattern a region several centimeters wide without loss of resolution by expanding
the image. The more complex scrolling DMDs can pattern areas as large as 60 cm without loss of
resolution, as the exposure head moves over a wide surface with scrolling images.
After patterning, a new fresh layer of photosuspension must be applied. This step can be done
by applying a liquid coating on the top with a blade. On other devices, the fresh layer can be
applied from the bottom. Another device dips the partially completed build into a suspension.
The most common light sources are UV lasers, UV and blue LEDs, and visible light. Ceramic
stereolithography can be accomplished in a conventional commercial SLA machine by replacing
the polymer resin with a suitable photopolymerizable ceramic suspension. However, several in-
vestigators and companies have produced purpose-build devices for ceramics. These devices can
be relatively compact machines aimed at prototype or small runs of small parts, such as the Lithoz
CeraFab 7500 (Lithoz GmbH, Vienna) and the 3DCeram FCP (3DCeram, Limoge), or quite
large robust machines aimed at industrial production, such as the CTC6060 (DDM Systems,
Atlanta).
The minimum feature size in the build direction (z) depends on the layer thickness h. To build
a part with a height H in the build direction requires n layers, where n = H/h. Relatively small
objects require hundreds or a few thousand layers. Large parts, such as 1-m-tall industrial gas
turbine cores, may have 10,000 layers. The build time scales with n because each layer requires
application of fresh liquid in a recoat step, which requires a certain time trecoat , typically 1060 s,
and because patterning also takes a certain time twrite , which requires a similar amount of time:

n
tbuild = ntrecoat + twrite,i = n(trecoat + twrite,ave ), 1.
1
where twrite,ave is the average time for writing a layer. For patterning with laser scanning, the write
time depends on the laser power and the energy dose needed for polymerization, which controls
the scanning speed for the laser. Scan speed is usually very fast, but if the dose is high and the laser
power is low, scan speed can be rather slow. The time to write each layer depends on the area to
be polymerized, and polymerization can be quite different for various layers in the design (38).
For patterning with a fixed DMD, the write time is typically the same for all layers and depends
on the power of the illumination and on the dose of radiation required for polymerization.
PRACTICAL FUNDAMENTALS OF PHOTOPOLYMERIZATION

OF CERAMIC SUSPENSIONS
All these devices operate by solidifying selected areas of the liquid by polymerization, so the
phenomena associated with photopolymerization of ceramic suspension are common to all of them.
Of primary interest to this review are the following practical fundamentals: (a) what determines
the width and depth of the exposed feature (line or pixel); (b) how the depth and width of the
exposed feature after polymerization depend upon energy dose and on the photoproperties of the
suspension; and (c) how the photoproperties of the suspension depend on the nature of the ceramic
powder, the active agents, and the inert dyes. In most cases, the monomer in the cured layers is
not fully polymerized. There is a variation in the extent of polymerization with vertical position
in the layers, which can be considered to be a cure profile. The variation of the cure profile with
exposure conditions is discussed below for the case of single layers.
During patterning, photoinitiators are activated in the illuminated areas. Photoinitiators typ-
ically create free radicals, which initiate the polymerization of the monomers. The extent of
polymerization () increases with illumination until the suspension reaches the gel point, at which
it is a soft solid ( = gel ). The intensity of the light attenuates as it propagates into the depth
beneath the surface (depth z), so the energy dose received at each depth [E(z)] varies. The depth
at which the gel point occurs is the cure depth (Cd ). The cure depth is the depth z at which the
energy dose suffices to bring the degree of polymerization to the gel point ( gel ), and the energy
dose at that depth is the critical energy dose Ec .
The relationship between the cure depth Cd and the applied energy dose E is expressed by

E
Cd = Dp ln , 2.
Ec
where the parameter Dp , which has units of length, is related to an attenuation length. The
practical behavior of the photosuspension is determined by the magnitude of the critical energy
Ec , which is the minimum energy required to initiate the polymerization and the magnitude of the
attenuation length parameter Dp . Equation 2 defines the working curve that is used to control the
polymerization depth. Figure 6 has measurements for the cure depth Cd as a function of energy
dose E, plotted according to Equation 2 so that the Dp parameter can be measured from the slope
and the Ec parameter can be obtained from the energy dose intercept. These measurements were
taken for suspensions containing 60-vol% SiO2 powder in a hexane diol diacrylate suspension
containing variable amounts of ketone photoinitiator and triazole dye. Notice that the slopes,
10.8 Halloran
3,000
2,500
0.5% PI
2,000 0% UV absorber
Cure depth, Cd (m)
Dp = 1,010 m
Ec = 19 mJ cm2
1,500
1,000 3% PI
0.15% UV absorber
Dp = 188 m
Ec = 25 mJ cm2
500
0
1 10 100 1,000
Energy dose, E (mJ cm2)
Figure 6
Cure depth versus energy for suspensions containing 60-vol% SiO2 powder in a hexane diol diacrylate
suspension containing variable amounts of ketone photoinitiator (PI) and a triazole dye.
which are the Dp values, are quite different for the two formulations, as are the Ec values from the
intercepts. It is useful to understand how these important parameters depend on the formulation
of the suspension, the photoinitiators and dyes, and the nature and amount of the ceramic powder.
The cure depth parameters can be expressed in terms of the concentration of the photoinitiator
(39, 40). The influence of other contributions on Dp can be accurately modeled by a simple atten-
uation model (40). The attenuation model is expressed in terms of the attenuation by absorption
of UV photons and by scattering of photons, which redirects photons from the forward beam
(with the scattered photons broadening the beam). The critical energy dose is modeled with an
inhibitor exhaustion model (40), which assumes that the critical energy is the minimum dose
needed to overcome native inhibitors so that free radicals can be available for polymerization.
Attenuation Length Parameter Dp

The attenuation model describes Dp as an attenuation length. As the UV beam passes beneath
the surface, it is attenuated by absorption from inert dyes (which simply absorb photons) and
photoinitiators (which absorb photons and generated free radicals). Absorption depends on the
concentrations and extinction coefficients of the absorbing species. The UV forward beam is also
attenuated by scattering from the particles, which depends on the ceramic volume fraction, particle
size, and the refractive index difference between the ceramic and the liquid. The attenuation
coefficient is 1/Dp :
1
= S + (1 )(P c P + D c D ), 3.
Dp
where is the ceramic volume fraction in the suspension; cP and P are the concentrations of the
photoinitiator; cD and D are the concentration and molar extinction coefficient of the dye; and
S describes the effects of light scattering, which is related to the inverse of the scattering length.
There is no simple closed-form expression for scattering length in concentrated suspensions. For
ceramic suspensions, S is experimentally found (41, 42) to increase with ceramic volume fraction
until it reaches a maximum at a volume fraction max . This behavior can be empirically fit to
obtain an approximate expression for S():

S() = 2 , 4.
2max
where is a fitting parameter that depends strongly on the refractive index difference between the
ceramic and the liquid. This approximation allows for an expression for the attenuation coefficient
that includes the volume fraction ceramic powder:

1
= P c P + D c D + ( P c P D c D ) 2 . 5.
Dp 2max
Figure 7 compares the prediction of the attenuation model (Equation 3) with measured values
for a number of SiO2 suspensions cured with two different UV sources. The predicted values use
data for the extinction coefficients from spectrophotometry. The agreement is satisfactory.
For a constant dose, the cure depth Cd varies as 1/(n)2 , where n is the refractive index
contrast, the difference in refractive index between the powder and the liquid n n0
= ncernn
0
0
.
An example is shown in Figure 8 for the case of SiO2 in aqueous media of varying refractive
indexes (40). Photopolymerization works well for ceramics with low refractive index (like SiO2 ) or
medium refractive index (like Al2 O3 ) but is more difficult for materials with high refractive index
(like lead zirconate titanate) (43, 44), for which scattering lengths are very short. The expressions
above are for UV-transparent ceramics. Some ceramics, such as SiC or TiO2 , are opaque at
1,200
60-vol% UV laser
1,000 50-vol% UV laser
60-vol% UV lamp
800
Predicted Dp (m)
600
400
200
0
0 200 400 600 800 1,000 1,200
Measured Dp (m)
Figure 7
Values of the attenuation parameter predicted from the attenuation model (Equation 3) compared with
measured values for 60-vol% SiO2 cured with a scanning UV laser (red circles), 50-vol% SiO2 cured with a
scanning UV laser (blue triangles), and 60-vol% SiO2 cured with a medium pressure mercury UV lamp
( yellow squares).
10.10 Halloran
800
700
Cure depth, Cd (m) 600
500
400
50-vol% SiO2 in
aqueous solution
300
200
100
0
0 20 40 60 80
Refractive index contrast, (n)2
Figure 8
Cure depth at constant dose for 50-vol% suspensions of SiO2 powders, measured in acrylamide solutions in
water and ethylene glycol, with the refractive index modified with ethylene glycol concentration. Cure depth
is inversely proportional to the square of the refractive index difference between the SiO2 and the solution.
UV wavelengths and so are strongly absorbing. Absorption lengths can be very short in opaque
ceramics, so photopolymerization cannot be easily done.
Critical Energy Dose Parameter Ec

The second parameter in the working curve is the critical energy dose Ec . Polymerization occurs
when radicals created by the photoinitiator are present in sufficient quantity to initiate the poly-
merization reaction of the monomers. But commercial monomers are stabilized against premature
polymerization by the addition of inhibitors, whose function is to remove free radicals. Oxygen
often acts as an inhibitor, particularly near the surface, where oxygen is absorbed from the air.
A model for Ec was based on the presumption that, for UV doses smaller than Ec , the smaller
number of free radicals created when a photoinitiator molecule absorbs a photon at low doses are
consumed by inhibitors so that polymerization does not occur. This model also considers absorp-
tion of photons by inert dyes. The hypothesis of this model for critical energy is that Ec is given by
the dose of UV photons that are not absorbed by inert dyes and that produce a population of free
radicals large enough to exhaust the population of inhibitors in the monomer solution to provide
surplus free radicals to begin the polymerization reaction. The critical energy then depends upon
the number and effectiveness of inhibitors, on the concentration and absorption coefficients of
inert dyes that absorb photons, and on the concentration and absorption coefficients of photoini-
tiators that create free radicals when they absorb photons. The ceramic powder plays a passive
role by diluting the active monomer and an active role by limiting photon penetration depth by
scattering. The critical energy dose can be approximated by
h 1
Ec = (1 ) (Q Q + O O + D c D ) . 6.
P c P
100
90
80
70
0.2% UV absorber
60
Ec (mJ cm2)
50
40
30
20
0% UV absorber
10
0
0.0 0.5 1.0 1.5 2.0 2.5
cPI2
Figure 9
Critical energy dose for Al2 O3 suspensions in acrylate monomers as a function of the inverse concentration
of ketone photoinitiator (PI).
Here h/ is the photon energy and quantum efficiency; is the ceramic volume fraction; cP
is the concentration of the photoinitiator; cD is the inert dye concentration, with D describing
the effectiveness of removing photons by dye absorption; and Q is the concentration of quinone-
type inhibitors and O is the concentration of oxygen inhibitors, with Q and O the effectiveness
of removing radicals by these two inhibitors. More details are available in the original paper
(41). We expect from Equation 6 that the critical energy dose should be inversely proportional
to the photoinitiator concentrations. This prediction agrees with the observations in Figure 9,
which shows the critical energy dose for Al2 O3 suspensions in acrylate monomers, as a function
of the inverse concentration of ketone photoinitiator, at two different levels of inert dye. The
observations fit well enough to make Equation 6 a useful model.
LINE WIDTH AND BROADENING FROM SIDE-SCATTER

In the absence of scattering, the profile of the cured line reflects the intensity distribution of the
beam. A laser beam with an ideal Gaussian lateral intensity distribution has a bullet-shaped cured
line. For ceramic suspensions, the cured line shape deviates significantly from the lateral intensity
distribution of the beam. Cured lines in ceramic suspensions can be broader and mushroom shaped
(17, 45). Some of these shapes are illustrated in Figure 10, which shows an experiment by Gentry
(46), in which a square beam of UV illuminated a SiO2 suspension through a glass slide. After
sufficient energy dose, the shape of the cured line profile was observed. The refractive index
contrast of the monomer solution was modified. With low refractive index contrast, the cured line
has the same width as the slit, but significant broadening occurs if the refractive index contrast
is high. The resolution of small features during patterning can be no better than the resolution
projected from the bit map, but it can be degraded by broadening. Ceramic suspensions can suffer
excess broadening, which degrades feature resolution. For laser scanning, the excess broadening
10.12 Halloran
a b c d e f
Schematic of curing Low RI contrast Low RI contrast Low RI contrast High RI contrast High RI contrast
E0 = 54 mJ cm2 E0 = 203 mJ cm2 E0 = 608 mJ cm2 E0 = 203 mJ cm2 E0 = 608 mJ cm2
Area illuminated
Glass slide
500 m
Cured polymer
line adhering to
slide
Figure 10
Shape of the cured line in SiO2 suspensions with varying refractive index (RI) values for monomer solution. Panel a illustrates how a
square-wave beam from a slit propagated into the suspension through a glass slide cures a broadened line. The cured line shape is
similar to the square wave with low RI contrast (panel b) but is increasingly broadened with higher RI contrast (panels cf ). The scale
bar (500 m) applies to panels bf. Adapted from Reference 46.
is related to the energy spread of a Gaussian beam (1), which is exacerbated by scattering (47).
With DMD projection, the broadening phenomenon is different, and the broadening can depend
upon the feature size and upon cure depth and dose (48). For square-wave illumination, the excess
broadening is the product of a characteristic width (the width sensitivity) and the logarithm of the
ratio of the energy dose and a width critical energy (49). Excess broadening is not important for
shallow cure depths but becomes important for deeper cure depth. There is less broadening in
highly absorbing suspensions, such as those with a high photoinitiator or inert dye concentration.
Excess broadening is more severe for high-refractive-index ceramics.
Jacobs (1) addressed the line width for laser-scanned stereolithography for the case of a beam
with a Gaussian intensity distribution of width W0 . The width of the cured region measured at
the surface, w cure , is related to energy dose Emax , to the critical dose Ed , and to the Gaussian beam
width W0 by

Emax
wcure = 2W 0 ln . 7.
Ec
Ceramic suspensions differ because scattering of the forward beam directs some UV radiation away
from the forward direction by side-scattering. Photopolymerization by the side-scattered beam
causes additional broadening. Hinczewski et al. (47) have proposed an empirical modification of
Equation 6 for the line width of ceramic suspensions, cured with Gaussian beams, which fit three
ceramic suspensions containing Al2 O3 , zircon (ZrSiO4 ), or SiO2 .
Gentry & Halloran (49) observed that the broadening illustrated in Figure 10 can be described
with a Beer-Lambert absorption of the side-scattered beam. An excess width (w ex ) due to broad-
ening is defined as one-half the difference between the measured line width (w) and the width due
to the illumination (wbeam ):
w wbeam
wex = . 8.
2
The relationship between the energy dose E0 and the excess broadening can be described with a
quasi-Beer-Lambert relationship:

E0
wex = Dw ln , 9.
Ew
1,750
1,500
1,250
Cure distance (m)

1,000 Db
750
Cd Wex
500
250
0
1 10 100 1,000
Energy dose (mJ cm2)

Figure 11
Cure depth (Cd , teal ) and excess width (w ex , yellow) as a function of energy dose for a 40-vol% SiO2
suspension in hexane diol diacrylate with 0.05 mol/L of a ketone photoinitiator. The broadening depth (Db )
is also indicated.
where Dw is considered the width sensitivity, the resin sensitivity parameter for side-scattered light.
The parameter Ew is the width critical energy dose (critical energy for polymerization in the hori-
zontal direction). This behavior arises because the suspension is a Beer-Lambert absorber, so poly-
merization from the horizontal beams from scattering would be similar to polymerization by the
forward beam. Thus, the broadening behavior would also fit a semilogarithmic model. Figure 11
shows the cure depth and excess width as a function of energy dose for a SiO2 suspension. The
width cure parameters (Dw , Ew ), however, are not the same as the cure depth parameters (Dp ,
Ec ). The broadening parameters (Dw , Ew ) that describe excess width vary with the amount of
scattering by ceramic particles and with the factors that affect the absorption and critical energy
dose of the monomer solution.
Scattering depends on the refractive index difference between the ceramic powder and
monomer, the solid loading of the ceramic suspensions, and the size distribution. The photoini-
tiator and dye determine the depth sensitivity and critical energy dose of the monomer solution.
Broadening by side-scatter can be described in terms of broadening depth Db , which is the
magnitude of cure depth Cd at the onset of broadening (where E = Ew ). In terms of the suspension
parameters,

Ew
Db = Dp ln . 10.
Ed
Db varies with the logarithm of the refractive index contrast (n/nq ) and can be fit to an expression
of the form

n/n0
Db = B1 ln , 11.
B2
where B1 is broadening strength and B2 is a broadening index. The broadening strength describes
how much the broadening depth changes with refractive index difference. A small value of B1
indicates a small change in the broadening depth with refractive index difference, whereas a large
value of B1 indicates a large change in the broadening depth with refractive index difference. The
experimental values of B1 and B2 depend on, for example, the photoinitiator concentration and
incident intensity.
10.14 Halloran
1,400
1,200
SiO2
1,000
Db (m)
800
600
400
Al6Si4O13
200 Al2O3
ZrSiO4
0
0.001 0.01 0.1 1
n/n0
Figure 12
Effect of refractive index contrast (n/n0 ) on the broadening depth (Db ), as measured for suspensions
containing SiO2 , Al6 Si4 O13 , Al2 O3 , and ZrSiO4 powders.
Figure 12 shows measurements for the broadening depth, from suspensions with three powders
of different refractive indexes in the same monomer solution, plotted as a function of the logarithm
of the refractive index difference. The refractive index of SiO2 is close to the refractive indexes of the
acrylate monomers, so the broadening depth is large for the SiO2 suspension (1,040 m). It is possi-
ble to use cure lines up to 1 mm deep with SiO2 before excess broadening becomes a problem. The
broadening depth is 285 m for mullite (Al6 Si4 O13 ) and 143 m for Al2 O3 . ZrSiO4 has a higher re-
fractive index, so broadening occurs even at a rather shallow cure depth of 55 m. Similar behavior
is observed with SiO2 suspensions when the refractive index of the monomer solution is changed.
Cure Profile: Variation of Monomer Conversion with Depth

Attenuation occurs below the surface, so the energy dose received by the suspensions varies with
depth (z) as E(z). The degree of polymerization, or monomer conversion, depends on the energy
dose [(E)], so monomer conversion can vary with depth. This variation in monomer conversion
leads to a nonuniform cure profile, (z). Such uniformity can be concerning when a large, complex
object is being built from hundreds of sequential layers. There is no simple expression for the
variation of monomer conversion with dose (E), but the relation between conversion and dose
is typically sigmoidal (5052), similar to what is shown in Figure 13. The suspension behaves
as a liquid (50) for small doses, for which the monomer conversion is less than the gel point
( gel ), 20% monomer conversion. We can identify the dose at which the suspension gels as the
familiar critical energy dose Ec , so (Ec ) = gel . The monomer conversion increases with dose,
and the polymer gel stiffens as the degree of polymerization increases. Eventually, reaches an
asymptote at maximum monomer conversion max , which is usually 80% monomer conversion.
Physically, max corresponds to the point at which the reaction freezes because the glass transition
temperature of the gel reaches ambient temperature. The maximum monomer conversion occurs
at some energy dose Emax , where (Emax ) = max . Further illumination for doses larger than Emax
does not cause further reaction, because the kinetics are too slow (although the reaction is not
complete).
100
Degree of monomer conversion (%)

80
max
60
40
20
gel
0
Ec Emax
Energy dose, E
Figure 13
Degree of monomer conversion versus energy dose.
The top surface of a cured layer has = max . The bottom of a layer (z = h, the layer thickness)
cannot be polymerized much beyond gel , or else unwanted solid is cured under the layer, a con-
dition known as print-through, which degrades the fidelity of the build. Thus, a stereolithography
build, including hundreds of layers, can have within each layer a nonuniform cure profile. This
nonuniformity can cause difficulties, such as cracking before or during binder removal, during
subsequent processes (53, 54, 56). As dimensional shrinkage accompanies polymerization, serious
distortions or stresses can develop (36).
Consider now the subsurface energy dose as it attenuates with depth beneath the surface, E(z),
which for a Beer-Lambert absorbing system is

z
E(z) = E0 exp ,
Dp
where E0 is the surface dose and Dp is the sensitivity of the suspension. Figure 14a illustrates vari-
ation of dose with depth for sensitivities ranging from a low-value Dp = 50 m, which attenuates
over a short distance, to a large-value Dp = 100 m, which has much less variation in dose through
the thickness. Combining E(z) with (E), fit to typical values for a SiO2 suspension, Figure 14b is
the approximate cure profile for a suspension with Dp = 1,000 m that has received four different
doses ranging from 100 to 700 mJ/cm2 . This would be the case for curing a layer in which the
solid lies over uncured liquid (such as an overhanging feature). Superimposed onto Figure 14b is
a vertical dashed line for a particular depth z = 100 m, which is the layer thickness in this case.
Also shown are horizontal dashed lines for E = Ec , below which the suspension is a liquid ( <
gel ), and E = Emax , above which the reaction is frozen and the degree of monomer conversion is
max .
Dose versus depth can be combined with monomer conversion versus dose to illustrate the
trade-off associated with the choice of surface dose E0 and layer thickness for a given sensitivity
Dp . Figure 15 shows the calculated degree of monomer conversion versus depth for a suspension
with a Dp of 100 m and three surface doses: 100 mJ/cm2 (E1 ), 300 mJ/cm2 (E2 ), and 500 mJ/cm2
(E3 ). At the highest dose (E3 ), the monomer is fully cured and therefore uniform to below the
100-m layer. However, an additional 80 m were partially cured below the layer, so this case
10.16 Halloran
1.0 500
a 0.9
b 450
Dp = 1,000 m
Fraction of initial dose, E(z)/E0
0.8 400 E4 Layer
Energy at depth Z, E(z)

thickness
0.7 Dp = 500 m 350
E3
0.6 300
0.5 250
Emax E2
Dp = 200 m
0.4 200
0.3 150
0.2 100 E1
Dp = 50 m
0.1 50
Ec
0.0 0
0 50 100 150 200 250 300 0 50 100 150 200

Depth, Z (m) Depth, Z (m)
Figure 14
(a) Normalized energy versus depth in micrometers for several different values of sensitivity Dp . (b) Energy versus depth for a given Dp
for several values of surface dose E0 , for doses 100 mJ/cm2 (E1 , teal ), 300 mJ/cm2 (E2 , blue), 500 mJ/cm2 (E3 , red ), and 700 mJ/cm2
(E4 , yellow).
is badly overcured. This case would degrade resolution by print-through. Regarding the E2 dose,
there are 30 m of solid beneath the layer, so the monomer is slightly overcured, and there are
also 30 m of solid material within the layer that has excess residual monomer. There is some
undercuring. For the lowest dose (E1 ), there is an 50-m region of undercured solid near the
surface, with a liquid layer beneath the solid.
POSTBUILDING OPERATIONS
After the final layer is cured, a number of important processing steps remain. The parts must
be collected from the build volume in a harvesting operation, and any uncured suspension must
be removed in a cleaning operation. Harvesting is simple for single objects (like Figure 2),
100
Layer
90
thickness
80
max
Degree of monomer
70
conversion (%)
60
50
40 E1 E2 E3
30
20
gel
10
0
0 50 100 150 200
Depth, Z (m)
Figure 15
Schematic of conversion versus depth for three surface doses E0 of 100 mJ/cm2 (E1 , blue), 300 mJ/cm2 (E2 ,
red ), and 500 mJ/cm2 (E3 , yellow) for a suspension with Dp = 100 m.
which need only be removed from the build platform. A design-like lattice in Figure 2 is self-
supporting, so there are no ancillary support structures to remove. Cleaning is easy, particularly
in this case, in which the fresh suspension is applied from the bottom. Designs such as the core
in Figure 3b require a more elaborate harvesting procedure. This complex shape has several
non-self-supporting features, and the ancillary support structures must be carefully removed.
Also, for this case, this core was built along with dozens of other objects in a large build volume,
whereby different objects were nested around others in the build. Harvesting this core involved
disassembling the nest of sibling builds. The cleaning operation was also more difficult for the
Figure 3 cores because uncured suspension had to be removed from the small holes and channels
without harming the thin posts and sections. Clearing the uncured suspension from the many
small passages between the struts of the Luneburg lens (Figure 4) also required care.
After the object is harvested and cleaned, it is ready for binder burnout and sintering. The
cured polymer is removed by pyrolysis during binder burnout. The binder burnout process is
similar to other ceramic forming methods that use a high level of binder systems, like multi-
layer ceramic capacitors and injection molding (34, 35). The challenges of binder burnout de-
pend on the section thickness. Binder burnout is relatively easy if the minimum section size
is a few millimeters and is more of a challenge if the section size is several centimeters. With
ceramic stereolithography, some additional concerns involve light curing strategy (cure pro-
file) (56) and residual monomer content (53). When pyrolysis is complete and all the residue
from the polymer is removed, the rest of the sintering process is the same as any other ceramic
process.
INDUSTRIAL-SCALE ADDITIVE MANUFACTURING

BY STEREOLITHOGRAPHY
Stereolithography can produce complex and sophisticated ceramic objects, but can it be used to
manufacture ceramic products? Ceramic stereolithography may be effective as a toolless forming
method for small production runs. In this case, Ceramic stereolithography is accomplishing
what could be done by ceramic injection molding, but without the cost and delay to acquire
hard tooling. However, considering only tooling undervalues the technology because molding
has significant shape limitations. The value of ceramic stereolithography, or any AM process,
is enabling the production of designs that cannot be molded or otherwise fabricated. These
unmoldable designs are often never considered, because traditional design practice penalizes
shapes that cannot be easily molded.
The ceramic core in Figure 3a was built by stereolithography, but its design was based on
contemporary commercial cores that are manufactured by conventional injection molding. Many
of the features of this core could have been achieved by molding, so the benefit of AM in this case
is that it enables toolless manufacture of a part that could be produced with injection molding
tooling. Toolless manufacturing is an attribute of AM that is important for early applications,
but it is perhaps not as important as the ability of AM to produce designs that are impossible to
manufacture with injection molding. An example of the latter is the demonstration part shown in
Figure 5 with 168 intertwined helical coils that are coiled to a tight pitch.
AM methods should be compared with ceramic injection molding, the traditional method used
to manufacture elaborate shapes. On a per-part basis, ceramic injection molding is much faster.
Forming cycle times for ceramic injection molding range from several seconds for small parts to
several minutes for parts as large as industrial gas turbine cores. If productivity is measured on
the basis of cycle time alone, ceramic stereolithography might seem to be impractical for mass
production of identical products. However, although completing all the layers in a platform can
10.18 Halloran
take hours, the platform can include a large number of parts, so the cycle time per part can be
much shorter. Also, an injection molding tool with one set of dies can produce only one type of
object without switching to a new set of dies. The platform of an AM tool can simultaneously
produce many different products. Cycle time alone does not capture the value of one ceramic
stereolithography tool simultaneously producing a variety of different products. Different concepts
of productivity are needed to compare conventional hard-tooled methods, which can make only
one part, with AM manufacturing tools, which are essentially flexible.
AM manufacturing is only now emerging, so there are no hard data on practical manufacturing
at the time of this writing. Every product category can be a different case. Consider only the
manufacture of airfoil cores, which are usually injection molded. Conventional injection molding
requires die sets for each product, and molding tooling die sets typically involve investments on
the order of $100,000 and acquisition delays of several months.
AM for Parts Conventionally Manufactured by Injection Molding

Stereolithography requires no tooling, which thus provides an advantage for relatively small pro-
duction runs. But for very large production runs lasting many years, manufacturing with hard-
tooled conventional injection molding could be advantageous. However, ceramics are abrasive.
Tool life can be much shorter for ceramic injection molding than for plastics injection molding.
A full analysis of ceramic injection molding cost needs to consider replacement or refurbishing of
tooling. Also, as the tools wear with use, there can be subtle but significant changes in quality. For
products like ceramic cores, with elaborate designs and tight dimensional tolerances, the quality
of cores molded in new tools can be different from that of cores molded with worn tools or cores
molded with refurbished tools. This difference in quality may affect product yield, which is as im-
portant as cycle time in determining productivity. There is no tool wear with stereolithography,
as every part is an identical digital copy of the master CAD design.
However, for large production runs, replacing conventional injection molding with AM is
a challenge because all currently commercial ceramic cores now being produced by injection
molding come from the restricted set of designs that are moldable. As injection molding is currently
the only manufacturing method, all existing designs are of course capable of being produced by
injection molding.
AM for Designs that Cannot Be Manufactured by Injection Molding

Not every product design can be molded. Although, in the context of ceramic forming, we often
think of injection molding as having excellent shape capability, the actual shapes that can be molded
are in fact rather limited. There must be sprues and runners, and the material must flow into every
location of the part, which imposes certain geometrical restrictions. Part geometry is even more
restricted if only two-part dies are considered. More difficult shapes require multipart molds, which
are much more costly. But even multipart molds have limitations. Now manufacturers advise their
customers against unmoldable designs or resort to assemblies of molded subcomponents. But
there are sound technical reasons why airfoil designers would like to use unmoldable cores with
impossible features. These difficult cores can enable more effective airfoils, and the performance
of the ultimate product (the turbine engine) can be improved with ceramic core designs that
are impossible to mold. Ceramic stereolithography has the potential to enable impossible airfoil
designs. The value of what might be enabled will contribute to what will emerge as the true
productivity of ceramic stereolithography.
CONCLUSIONS
Ceramic stereolithography refers to a number of AM methods involving patterning by photopoly-
merization of ceramic powders suspended in a polymerizable medium. A broad range of ceramic
stereolithography techniques have been reported, and several effective devices are commercially
available. A diverse range of ceramic prototypes and functional parts have been reported, particu-
larly for ceramics with low refraction index. The practical fundamentals of suspension photopoly-
merization can be understood by using relatively simple physical principles. The relation between
the desired cure depth and the necessary energy dose depends on the attenuation of the beam in the
suspension and on the nature of the monomer and added polymerization inhibitors. Attenuation
in the suspension can be understood in terms of absorption, which involves the concentration and
extinction coefficients of dyes and photoinitiators, and in terms of scattering by ceramic particles,
which involves the volume fraction and refractive index of the ceramic. The width of a cured
feature depends on the lateral intensity distribution, with excess broadening caused by scattering,
and so is related to the refractive index of the ceramic. The cure profile, or the fractional monomer
conversion within each layer, can be described in terms of both the attenuated dose at each depth
and the relation between dose and monomer conversion.
DISCLOSURE STATEMENT
The author is a cofounder of DDM Systems, Inc.
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Fabricación de Aditivos para Cerámica Por Fotopolimerización

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MR46CH10-Halloran ARI 8 March 2016 14:22

V I E W Review in Advance first posted online

still occur before final publication

Annu. Rev. Mater. Res. 2016. 46:10.110.22 Keywords

This articles doi: Abstract

Photopolymerization is not a new ceramic process. Photopolymerized tape casting systems

www.annualreviews.org Ceramic Stereolithography 10.3

PROCESSING BEFORE PATTERNING

www.annualreviews.org Ceramic Stereolithography 10.5

BUILDING MULTILAYER OBJECTS

for recoat and for exposure.

www.annualreviews.org Ceramic Stereolithography 10.7

PRACTICAL FUNDAMENTALS OF PHOTOPOLYMERIZATION

Attenuation Length Parameter Dp

www.annualreviews.org Ceramic Stereolithography 10.9

Cure depth, Cd (m) 600

Critical Energy Dose Parameter Ec

www.annualreviews.org Ceramic Stereolithography 10.11

LINE WIDTH AND BROADENING FROM SIDE-SCATTER

www.annualreviews.org Ceramic Stereolithography 10.13

Cure distance (m)

Energy dose (mJ cm2)

Cure Profile: Variation of Monomer Conversion with Depth

www.annualreviews.org Ceramic Stereolithography 10.15

Degree of monomer conversion (%)

0.8 400 E4 Layer

Energy at depth Z, E(z)

0 50 100 150 200 250 300 0 50 100 150 200

www.annualreviews.org Ceramic Stereolithography 10.17

INDUSTRIAL-SCALE ADDITIVE MANUFACTURING

AM for Parts Conventionally Manufactured by Injection Molding

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Austin: Univ. Tex.

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