Rapid prototyping of microstructured ceramic and metal parts

using reaction molding techniques

T. Hanemanna,b, K. Honnefb, J. Hausselta,b

a
Forschungszentrum Karlsruhe, Institut f. Materialforschung III, D-76021 Karlsruhe, Germany
b
Albert-Ludwigs-Universität Freiburg, Institut f. Mikrosystemtechnik (IMTEK), D-79110 Freiburg, Germany

Abstract

Different variants of reaction molding techniques like UV-embossing, UV-RIM, Photomolding, a.o., exploiting the
rapid light induced photopolymerization of reactive resins are widely used in microsystem technologies for the
fabrication of microoptical components or for rapid prototyping purposes. The solidification based on photocuring limits
the suitable materials to transparent resins and yields only plastic microstructured parts. In this paper the further
development of micro reaction molding with respect to a rapid prototyping of ceramic and metal parts will be
described. As in the different variants of powder injection molding additional process stages have to be considered
and individually optimized. First a free-flowing reactive resin based composite with a large filler load (microsized
ceramic or metal powder) of at least 45 vol% has to be prepared. The addition of suitable thermal initiators allows the
solidification of the composite subsequently after mold filling in a molding tool equipped with microstructured mold
inserts. The mold filling and hence the accurate reproduction of surface details depend strongly on the composite’s
viscosity, which is a function of the filler load. The further process stages like debinding and sintering have to be
optimized with respect to the polymer based reactive resin used and the ceramic filler. Especially an improved process
control of the composite formation prior to molding and the thermal debinding is crucial for the realization of ceramic or
metal parts carrying a microstructured surface. The development of the whole process chain and some
microstructured ceramic or metal parts will be presented.

Keywords: rapid prototyping, reaction molding, microstructured parts, ceramics, metals

1. Introduction

In the macroscopic world a whole family of different

rapid prototyping techniques has been established with
respect to a significant time-to-market reduction and
investment minimization [1,2]. The term “rapid
prototyping” is used for model generation using mainly
generative techniques (rapid prototyping, RP), mold
making applying generative and replication techniques
(rapid tooling, RT) and for small scale fabrication with
RP or RT methods (rapid manufacturing).
The first rapid prototyping of a microcomponent
was reported by Ikuta and Hitowatari in 1992 using a
variant of stereolithography [3]. In the last years the
microstereolithography was extended to the fabrication Fig. 1. Upper molding tool carrying microstructured
of structures with details in the nanometer range using mold inserts.
2-photon-polymerization [4, 5]. The commercialization
of micro- and nanostereolithography enables the the composite formation and ending with the final
fabrication of prototypes with micro- and nanostructures sintering step for a rapid prototyping of ceramic and
on service [6,7,8]. Due to the fundamental process metal microstructured parts will be described.
characteristics based on photopolymerization of
polymer reactive resins the different variants of 2. Reaction molding process development
stereolithography yield polymer microcomponents
mainly. Quite recently the microstereolithography of 2.1. Reaction molding of pure reactive resins
polymeric resins filled with ceramic particles has been The applied reaction molding (photomolding) setup
described [9, 10]. The rapid prototyping of metal in combination with laser assisted micromachining as
microcomponents can be realized using laser suitable master and mold insert tooling technique
microsintering of metal powders [11, 12] or layer based allows a rapid prototyping of microstructured
electrochemical fabrication methods, the latter method components. The development of different laser
has been commercialized [13]. A comprehensive assisted micromachining techniques like ablation and
overview describing the rapid prototyping of laser-micro-caving enables the fabrication of mold
microcomponents made of silicon, polymers, ceramics inserts made of polymers (PEEK, PSU, PI), metals
and metals will be published at the end of 2005 by (stainless steel, cemented carbides), ceramic (alumina)
Springer [14]. and silicon. Structural details down to the micrometer
range and aspect ratios up to 10 can be realized. The
In this work the process development starting with accessible surface roughness Ra is small enough for

Multi-material Micro Manufacture

W. Menz & S. Dimov
(C) 200X. Published by Elsevier Ltd. 1

Fig. 2. Mold insert carrying CE-chip micro-
structures for the measurement of the geometric
accuracy (replicated PMMA part as insert).
molding purposes (steel: 200-300 nm, alumina: 200
nm, PI < 100 nm). The fabrication of mold inserts using
laser assisted micromachining can be realized,
depending on the size and geometry of the
microstructure, within 3 working days. Reaction molding
technique uses polymer resins i.e. low viscous
monomer-polymer-mixtures like unsaturated polyesters
solved in polystyrene or methacrylates solved in their
monomers. Reactive resins can cured either thermally
or as in microstereolithography [2, 14] or in photoresists
via UV-light. The photomolding process uses a molding
equipment which shows some similarities to injection
molding (molding tool geometry, die plate, demolding
support, a.o.). More details to the mold insert
fabrication and the realizable microstructured polymer
parts were given in [15,16].
Some demolding problems after curing resulted in
a redesign of the upper molding tool carrying the
ejector back plate and in an increase of the number of
ejectors (see Fig. 1). The die plate contains two
microstructured mold inserts which are either fitted
directly into the molding tool (see Fig. 1, lower mold
insert) or by using an adapter for shims made of
different materials like steel, polymer foils or ceramic
substrates (see Fig. 1, upper mold insert, carrying
Table 1
Comparison of the measured fluidic channel widths
(average values)
Mold insert Mold [µm] Deviation [µm]/[%]
Pos. 1 206.3 ± 2 208.0 ± 2 1.7 / 0.8
Pos. 2 177.7 ± 2 179.7 ± 2 2.0 / 1.0
Pos. 3 188.5 ± 2 188.1 ± 2 0.4 / 0.2
capillary electrophoresis (CE) chip structures) [16]. The
ejector pins are located around the mold inserts as a
frame. During demolding the ejectors press against the
base plate which was generated during photocuring.
The microstructures are located on the base plate
between the ejectors. The molding cycle can be divided
into four process steps:
1. Closing and evacuation of the tool
2. Low pressure resin injection
3. Curing under applied dwell pressure
4. Demolding
Table 2
Filler specifications (*vendor´s data, **measured )
*Alumina *Alumina **Iron
CT3000SG TM DAR OM
Average 0.7 µm 0.2 µm 3.8 µm
particle size
Specific surface 7 m²/g 14 m²/g 1.2 m²/g
Volume specific 27 m²/cm³ 55 m²/cm³ 10 m²/cm³
surface
Fig. 3. Relative viscosity of alumina and iron
dispersed in unsaturated polyester UPM3.
The total height of the molded part (base plate and
microstructure), which depends on the mold inserts
used, is around 2 - 4 mm, a curing time around 5 min
yields. Due to the low resin’s viscosity the solidification
time is independent from the maximum aspect ratio on
the mold insert. The accurate reproduction of the
surface details was measured at a mold insert carrying
a capillary electrophoresis chip and the related PMMA
replica (see Fig. 2 and Table 1). Within the
experimental error the average geometric accuracy
measured at three different positions at the
microstructure of a series of replicated parts is better
than 1 %.
2.2. Composite formation
As in powder injection molding of micro-
components polymer-filler-composites (feedstock) have
to be prepared for replication and postprocessing to
obtain dense ceramic or metal parts [17]. The
submicron sized alumina TM DAR (Taimei) and the
micron sized iron powder OM (BASF) were selected as
ceramic and metal fillers. Due to the low viscosity of the
applied reactive resins it was possible to prepare the
composites using dissolver type stirrers under ambient
conditions. The generation of warp-free ceramic or
metal parts requires a solid load of at least 45 vol% in
the composite, larger loads result in a significant
viscosity increase and can be accompanied by a
incomplete mold filling and voids. To ensure that the
solidification to a stable greenbody can be realized
small amounts of an organic peroxide as thermal
initiator have to be added to the composite. The UV-
source in the reaction molding setup emits intense IR
2
 Fig. 4. Mold insert and replicated polyester-
alumina-composite greenbody (coated with thin
gold layer for SEM-investigation).

radiation which enables a thermally initiated poly-

merization.

3. Composite properties
As described a compromise between largest filler
loads and low viscosity has to be found. Therefore, a
systematic investigation of the composite’s viscosity
with the filler amount is essential for finding an
optimised composite. The resulting viscosity depends
on the particle size, the specific surface and more
accurately on the volume specific surface (see Table
2). In comparison to the iron the particle size of the
alumina is smaller by a factor of 20 and the related
specific surfaces are significantly larger.
The relative composite viscosity increases with
increasing filler amount (see Fig. 3). Especially at
higher filler loads the alumina composites show a larger
viscosity up to a factor of 10 under same conditions
(polyester resin UPM3, temperature 60°C and shear
rate 100 1/s) than the iron filled systems. A filler content
beyond 50 vol% can only be realized using the metal
powder.
4. Composite Molding
The reaction molding setup described earlier
allows for the molding of low viscous resin based
composites. (see Fig. 4). Due to the thermal
polymerization process and the decomposition
temperature of the peroxide around 60°C the composite
curing times are extended up to 30 min in comparison
to pure polymer resins. For a complete solidification the
greenbodies were tempered after demolding for several
hours at 90°C.
5. Debinding and sintering
A very precise process control of the debinding
step is essential for obtaining a dense and crack-free
ceramic or metal part. In case of metal containing
composites the debinding and sintering have to be
performed under inert gas atmosphere. The used
unsaturated polyester polymerizes to a thermoplastic
polymer and starts to decompose at temperatures
around 300°C independently from the used atmosphere
(see Fig. 5).
The alumina containing composites shows two
main decomposition steps: one in the temperature
range from 300°C to 400°C under air atmosphere and a
smaller one between 470°C and 510°C. Under
Ar-atmosphere the first weight loss process seems to
be slightly hindered. The temperature programme for
debinding has to consider the results obtained from
thermogravimetric investigations, details are given in
[18,19]. Especially in the temperature range with a
pronounced decomposition, here between 300°C and
Fig. 5. Thermogravimetric investigations on
unsaturated polyester/alumina composites.
Fig. 6. Sinter density of different unsaturated
polyester/alumina composites.
430°C, a small heating rate of 1 °C/min is necessary for
a crack-free microstructured component.
6. Sintering
The composite’s viscosity shows a significant
influence on the resulting ceramic or metal part density.
With increasing composite viscosity air bubbles are
trapped in the composite, which cannot be removed by
degassing. The sinter density is then lowered due to
voids in the bulk material. The viscosity of reactive
resins can be lowered by adding the related monomer,
in case of unsaturated polyesters styrene. The used
polyester based resins UPM2 and UPM3 differ in the
additional styrene content (UPM2: 20 wt%, UPM3:
40 wt%). The smaller diluent content yields a larger
composite viscosity at the same ceramic load and
smaller density values after sintering due to voids (see
Fig. 6).
In most cases UPM3 as reactive resin matrix
allows for larger accessible filler loads and higher
densities. The use of the nanosized TM DAR alumina
with the enlarged specific surface and the resulting
large sinter activity enables a sinter temperature
reduction from 1600°C to 1400°C, the microsized iron
powder sinters around 1300°C. Prototypes of ceramic
and iron microcomponents can be obtained in
reasonable quality (see Fig. 7). The measurement of
the CE chip channel at the same positions described in
section 2.1. shows a geometric accuracy better than
2% (alumina part).

3
 [9] Bertsch A, Jiguet S, Renaud P. Microfabrication of
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[10] Chartier T. Chaput C, Doreau D and Loiseau M.
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[11] Fischer P, Karapatis N, Romano V, Glardon R and
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Fig. 7. Images of sintered microstructured alumina infrared laser pulses with metal powders in selective
and iron parts. laser sintering. Appl. Phys. A, 74(4) (2002) 467-
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[14] Hanemann T, Bauer W, Knitter R and Woias P.
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Molding temp [°C] 25 30 - 60 sequence for the rapid fabrication of micro-
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Curing time [min] 2 - 5 min 20 – 30 [16] Pfleging W, Hanemann T, Torge M, Bernauer W.
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